B400 Physical Chemistry

Philippine Handbook Physical Chemistry
In Chemical Engineering
F. PHYSICAL CHEMISTRY
F.1. SOLID STATE
Solids have two common crystallographic forms, cubic and hexagonal, classified and
characterized based on the type of unit cell.
A unit cell is characterized by an array of lattice points in three dimensions, e.g., there are
three lattice points in a unit cell in three dimensions.
A crystallographic unit cell is a parallelepiped formed by connecting the eight lattice
points.
Cubic unit cell is characterized by the six square faces and the three equal non-coplanar
edges denoted as a, b and c. (i.e., a = b = c. !he volume of a cubic unit cell is"
V a
!
(f - #
Hexagonal unit cell is characterized by four rectangular faces with edges that are either
side ac or side bc, two parallelograms with equal sides (e.g., a = b and interior angles of
60
o
and 120
o
. !he volume of a hexagonal unit cell is abcsin(#$%
o
or
(f - $
F.1.1. Si"#le Cubic C$%&'al
!here are three types of cubic crystals" simple, face centered and body centered. &n simple
cubic crystal ('(( unit cell, there is one lattice point at each of the eight corners of a cube.
!his type of unit cells where there is lattice point only at the eight corners is called the
primitive type of unit crystal. An example of an '(( is shown in )igure ) - #. !he number of
lattice points in a given unit crystal is denoted by Z.
Figu$e F ( 1. *xample of 'imple (ubic (rystal
) - #
'uppose an atom of radius r occupies a lattice point and is tangent to all the ad+acent atoms,
there are six contacts wherein each of the unit cells, edges is the sum of two atomic radii.
!hus, an edge of a cubic crystal is equal to $r. !he volume, therefore, of a simple cubic
crystal is
V
c
)*$+
!
,$
!
(f - -
&n '(( there is only one host atom inside the cube because each of the eight corner atoms
contributes one eighth of an atom to the cell interior. !he volume of the cell occupied by the
atoms is
V
SCC
)-.!+ $
!
/. (f - .
!he packing eiciency of a lattice is defined as the ratio V
SCC
0V
c
1 thus, for the simple cubic
unit cell the pac/ing efficiency is about 0$..1.
F.1.*. 2o3% Cen'e$e3 Cubic C$%&'al
&n 2ody (entered (ubic (2(( unit cell there is one host atom at each corner of the cube and
one host atom in the center of the cube" 3 = $. *ach corner atom touches the central host
atom along the diagonal of the cube. !hus, the atoms at the lattice points are tangent to the
host atoms along the diagonal but not to each other, )igure ) - $. !he length of the edge of
the unit cell is $(.4-
#4$
and the volume of the cube is
V
c
)!*.!+)-.!+
1.*
$
!
(f - 0
Figu$e F 4 *. *xample of 2ody (entered (ubic (rystal
!he pac/ing efficiency in this type of lattice is about 561, which is much higher than that in
'((.
F.1.!. Face Cen'e$e3 Cubic C$%&'al
) - $
!ace Centered Cubic ()(( unit cell has one host atom at each corner and one host atom in
each face. !he corner atom contributes one-eighth of its volume while the face atoms
contribute half of its volume. !hus the face atoms contributions are equivalent to - atoms and
the corner atoms contribution is equivalent to one. !he total number of lattice points is ., i.e.,
3 =
#
4
6
.
6 7
#
4
$
.
5 = . ()igure ) - -.
Figu$e F 4 !. *xample of )ace (entered (ubic (rystal
!he corner and face atoms of this type of cubic crystal touch along the diagonal of the face
and are tangent to each other. !he unit length of )(( edge is equal to $
-4$
r. !hus, the volume
of the crystal is
V
c
)*
!.*
$ +
!
(f - 5
!his type of crystal has a pac/ing efficiency of about 8.1 and is the most closely pac/ed
among cubic crystals.
F.1.-. P$i"i'i5e Face Cen'e$e3 Cubic
&n any lattice it is possible to choose a primitive unit cell, i.e., 3 = #. !here are actually a
number of choices. All the primitive unit cells on a lattice have the same volume. 9owever,
only one of these primitive unit cells has the three shortest cell edges (a,b,c and this is the
&'an3a$3 $e3uce3 cell.

)or )(( lattice, the standard reduced cell is a $ho"bohe3$on, where a b c *$. !he
three interior angles formed between unit cell edges are denoted as"
angle between the edges b and c
angle between edges a and c
angle between edges a and b
)or )(( rhombohedral standard reduced cell, 67
o
. A cube is a special
rhombohedron where = = = :%
o
.
) - -
Figu$e F ( -. "#"$%
F.1.8. P$i"i'i5e Hexagonal
!he most densely pac/ed (i.e., least amount of empty space possible arrangement of spheres
is where each of the sphere touches six other spheres arranged in the form of a regular
hexagon, )igure ) - 0.

Figu$e F 4 8. ;ensely <ac/ed Arrangement of 'pheres
&f two of these hexagonall% clo&e&' #ac9e3 )HCP+ #lane& are stac/ed directly on top of one
another, the resulting unit cell is the primitive of the hexagonal crystal, )igure ) - 5.
Figu$e F 4 6. <rimitive 9exagonal =nit (ell
) - .
A primitive hexagonal unit cell as outlined by bold blac/ lines in the crossed stereo pair in
)igure # - 5, has cell edges a b *$ and c *$1 'hus, the ratio c0a 1. The pac/ing
efficiency of this three dimensional lattice is about 5%1 (compared to 8.1 for closest
pac/ing, even though the atoms are closest pac/ed in two dimensions.
Coordination in HCP
*ach host atom in a 9(< lattice is surrounded by and touches #$ nearest neighbors, each at a
distance of $r"
a. !here are six atoms in the planar hexagonal array (the central A layer>
b. !here are three atoms in the 2 layer above the A layer>
c. !here are three atoms in the 2 layer below the A layer.
!he six atoms in the two 2 layers form a '$igonal #$i&" around the central atom in the A
layer> the length of this prism is $
.
(<&'
.
r.
Figu$e F 4 :. TITLE
Bragg's Law and Diffraction
?aves can be used to reveal the atomic structure of crystals. !he principle that utilizes this
method is /nows 2ragg@s Aaw which refers to the simple equation
n & 2d sin (f - 8
!he variable d is the distance between atomic layers in a crystal, is the ;a5eleng'h of the
incident B-ray beam and n is an integer. !his observation is an example of B-ray ;a5e
in'e$<e$ence commonly /nown as B-ray diffraction (BC;, and was direct evidence for the
periodic atomic structure of crystals postulated for several centuries.
!he *nglish physicists 'ir ?.9. 2ragg and his son 'ir ?.A. 2ragg derived 2ragg,s equation
in #:#- to explain why the cleavage faces of crystals appear to reflect B-ray beams at certain
angles of incidence . !he 2raggs were awarded the Dobel <rize in physics in #:#0 for their
wor/ in determining crystal structures beginning with Da(l, 3n' and diamond. Although
2ragg@s law was used to explain the interference pattern of B-rays scattered by crystals,
) - 0
diffraction has been developed to study the structure of all states of matter with any beam,
e.g., ions, electrons, neutrons, and protons, with a wavelength similar to the distance between
the atomic or molecular structures of interest.
Bragg's Law
(onsidering the conditions necessary to ma/e the phases of the beams coincide when the
incident angle equals and the reflecting angle can easily be derived using 2ragg,s Aaw. !he
rays of the incident beam are always in phase and parallel up to the point at which the top
beam stri/es the top layer at atom z ()igure ) - 6. !he second beam continues to the next
layer where it is scattered by atom 2. !he second beam must travel the extra distance A2 7
2( if the two beams are to continue traveling ad+acent and parallel. !his extra distance must
be an integral (n multiple of the wavelength (l for the phases of the two beams to be the
same"
n & '( )(C (f - 6
Figu$e F ( ,. ;eriving 2ragg@s Aaw =sing the Ceflection
Eeometry and Applying !rigonometry
!he lower beam must travel the extra distance (A2 7 2( to continue traveling parallel and
ad+acent to the top beam.
Cecognizing d as the hypotenuse of the right triangle A2z, we can use trigonometry to relate
d and q to the distance (A2 7 2(. !he distance A2 is opposite q so,
'( & d sin * (f - :
2ecause A2 = 2(, eq. (f - 6 becomes,
n & 2'( (f - #%
) - 5
'ubstituting eq. (f - : in eq. (f - #%, we have
n & 2 d sin * (f - ##
and 2ragg@s Aaw has been derived. !he location of the surface does not change the derivation
of this Aaw.
F.*. =ASES
Eases are materials of very low density that must be enclosed to /eep together and have no
definite shape and volume, and completely fill a container. !hus, the volume of gases is the
volume of the container. Eases exert pressure on all sides of the container and can be
compressed by a pressure greater than the pressure it exerts on its container. !he term vapor,
fume, air, or miasma also describes a gas. Air indicates the common mixture of gases in the
atmosphere (i.e., oxygen and nitrogen and miasma is the bad-smelling or poisonous gas.
Fapor and fume suggest that the gas come from a particular liquid.
aseo!s "tate
&n the gaseous state, matter is made up of particles (atoms or molecules that are not
attached to each other.
!he intermolecular or interatomic force that holds solid and liquid molecules together
are overcome by the motion of the molecules in gases.
!he particles of gases have too much thermal energy to stay bound to each other.
!he motion and vibration of the atoms pull the individual molecules apart.
Eases consist mostly of unoccupied space. A gas molecule has to travel a long
distance before it encounters another molecule. &t can be pictured as having a @point
source of mass@, where the volume of the molecule is negligible compared to the space it
occupies.
?hen two gas molecules collide with each other they bounce off, ideally in a
completely elastic encounter. !here is pressure within the gas caused by the gas
molecules in motion stri/ing each other and anything else in their path. !he pressure that
a gas exerts on its container comes from the molecules of gas hitting the inside of the
container.
) - 8
!here are some materials that do not exist in the gaseous form because the amount of
molecular motion is not enough to pull the molecules apart. )or this reason it is unli/ely
for large biological molecules such as proteins, fats, and ;DA to appear the form of a gas.
Physical Properties Li#!id $ir
Aiquid air, with all the molecules touching each other, has a density of about %.680
grams per milliliter (g4mA.
Avogadro@s law states that one mole of any gas occupies a volume of $$.. liters at
standard temperature and pressure or '!< (# atmosphere pressure and %G(. At '!< gas
air weighs about $6.:5 g and occupies a volume of $$.. A or #.$: g4A.
Aiquid air is over 580 times denser than gas air at one atmosphere. !his means each
molecule of the gas has more than 580 times its own volume to move around.
F.*.1. I3eal =a& La; Fo$"ula
+, & n-" (f - #$
Eases may be completely described by its ma/eup, pressure, temperature, and volume as
shown in equation f H #$, where < is the pressure, F is the volume, n is the number of moles
of gas, ! is the absolute temperature, and C is the =niversal Eas (onstant. !he ideal gas la.
ormula is pretty accurate for all gases as the gas molecules are assumed as point masses and
the collisions of the molecules are totally elastic. A completely elastic collision means the
energy of the molecules before collision equals the energy of the molecules after collision, or
to put it another way, there is no attraction among the molecules.
!he ideal gas formula becomes less accurate as the compression increases and temperature
decreases. )or each gas, however, corrections can be introduced to both factors, which will
convert the &deal Eas Aaw )ormula to Ceal Eas Aaw )ormula. !he ideal gas formula can
serve as a good estimation of the way gases act.
!he =niversal Eas (onstant, C, can be expressed in several ways, depending on the units of
<, F, and !. !he commonly used value for C is %.%6$# liter - atmospheres per mol H degree
Ielvin. Cemembering this value for C and the &deal Eas Aaw )ormula is highly
recommended.
F.*.*. >ine'ic Molecula$ Theo$% o< =a&e&
) - 6
!hese statements are made only for what is called an ideal gas. !hey cannot all be rigorously
applied (i.e. mathematically to real gases, but can be used to explain their observed behavior
qualitatively.
All matter is composed of tiny, discrete particles (molecules or atoms.
&deal gases consist of small particles (molecules or atoms that are far apart in
comparison to their own size. !he molecules of a gas are very small compared to the
distances between them.
!hese particles are considered to be dimensionless points occupying practically zero
volume. !he volume of real gas molecules is assumed to be negligible for most
purposes. Ceal gas molecules do occupy volumes and have an impact on the behavior
of the gas.
!hese particles are in rapid, random, constant straight-line motion and can be
described by well-defined and established laws of motion.
!here are no attractive forces between gas molecules or between molecules and the
sides of the container with which they collide. &n a real gas, there actually is attraction
between the molecules of a gas.
Jolecules collide with one another and the sides of the container.
*nergy can be transferred in collisions among molecules.
*nergy is conserved in these collisions, although one molecule may gain energy at the
expense of the other.
*nergy is distributed among the molecules in a particular fashion /nown as the
Jaxwell-2oltzmann ;istribution.
At any particular instant, the molecules in a given sample of gas do not all possess the
same amount of energy. !he average /inetic energy of all the molecules is
proportional to the absolute temperature.
F.*.!. Dal'on?& La; o< Pa$'ial P$e&&u$e&
?hen the volume and temperature are held constant the ideal gas equation can be written as
P% kn where k &
&
'T
/ )rom the given formula, it is apparent that < is directly proportional to
the number of moles of gas in the container.
&n a mixture of gases, both the pressure and number of moles are additive. !o illustrate this
point, consider a two-gas system where <
#
is the partial pressure of n
#
moles of the first gas
and <
$
is for n
$
moles of the second gas. 'ince these gases occupy the same volume at the
same temperature, it follows that they have the same k value. &f n
!
and <
!
are the total
number of moles and pressure, respectively, then by definition
$ #
n n n
T
+
(f - #-
and
) - :
$ #
P P P
T
+
(f - #.
&f + & kn, then for the first gas +
1
& kn
1
and for the second gas +
2
& kn
2
. Adding the two
gives +
"
& k0n
1
) n
2
1 & kn
"
. !his relation can be extended to systems of gas mixtures where
there are n different or similar gases. !he relation is /nown as ;alton@s Aaw of <artial
<ressures, which says that K"he sum o all the partial pressures o the gases in a volume is
e*ual to the total pressure/K
F.*.-. =$aha"?& La; o< Di<<u&ion )o$ E<<u&ion+
?ith no change in pressure, gases can either diffuse in all directions from an original
concentration or effuse through a small hole and move into a mixture at a rate that is inversely
proportional to the square root of the formula weight of the gas particle. ;iffusion can be
imagined as a drop of in/, which has the same specific gravity as water, being carefully
placed at the center of a glass of water. !he in/ will diffuse in all directions from the point of
origin. !his mixing through diffusion is due to the movement of the in/ molecules in water.
Eases diffuse much more quic/ly than liquids because gases have higher energy of motion
and the available path for their unobstructed straight movement is greater.
!emperature is a type of energy. &t is the way we sense the motion of the molecules. !he
formula for energy of motion is E % ()* m +
*
. !his very motion of the molecules is the
driving factor in the mixing action of diffusion. !he mass of the molecule is the formula
weight or molecular weight of the gas. )rom the formula for energy of motion, it is evident
that the mass of the particle (the formula weight is inversely proportional to the square of the
velocity of the particle. !his is the easiest way to remember Eraham@s Aaw.
#
$
$
$
$
#
,-
,-
+
+
(f - #0
F.*.8. Real =a&e&
Jolecules attract or repel each other depending on the distance between molecules in
motion.
Jolecules collide with one another and the sides of the container.
*nergy can be transferred in collisions among molecules.
*nergy is conserved in these collisions, although one molecule may gain energy at the
expense of the other.
) - #%
*nergy is distributed among the molecules in a particular fashion /nown as the Jaxwell-
2oltzmann ;istribution.
At any particular instant, the molecules in a given sample of gas do not all possess the
same amount of energy.
!he average /inetic energy of all the molecules is proportional to the absolute
temperature.
F.*.6. C$i'ical Te"#e$a'u$e an3 P$e&&u$e
!he errors in ideal gas predictions become most stri/ing as you approach the gases, critical
conditions. At higher temperatures and4or higher pressures the difference between a gas and
a liquid eventually disappears and a supercritical fluid is formed. !he point at which this
happens is called the c$i'ical #oin'
DEFINITION
The highest temperature at which a species can coexist as a liquid and a vapor is termed its
critical temperature, Tc. On the other hand, the highest pressure at which a species can
coexist as a liquid and a vapor is termed its critical pressure, Pc.
DEFINITION
DEFINITION
Figure F 9 TITLE
) - ##
$ supercritical luid is a s!bstance that is abo+e its critical temperat!re. Tc and
press!re. Pc/
F.*.:. @on4I3eal EAua'ion& o< S'a'e
An equation of state relates the molar density (or specific molar volume of a fluid to the
temperature and pressure of that fluid. (Dote that the term fluid was used rather than gas
&irial E#!ations of "tate
A primarily mathematics motivated (theory is from statistical mechanics equations of state,
the virial equation uses a power series in the form"
(f - #5
where 2, (, and ; (etc. are material dependent constants. !hese constants are sometimes
difficult to determine (theoretically and the expression is typically truncated after the 2
values so that there is only one KfittingK parameter, (i.e.,
(f - #8
E
This expression is good for non-polar gases. The constant, B, can be obtained from the
following relation:
(f - 18)
where T
c
and P
c
are the critical temperature and pressure, and B
o
and B
1
are given by the
following expressions:
(f - 19)
(f - 20)
2einition
) - #$
The reduced temperature (pressure) is a dimensionless temperature (pressure) given as
the ratio of the actual temperature (pressure) to the critical temperature (pressure) and is
denoted by T
r
(P
r
).
DEFINITION
The Pitzer ascentric factor ( ) is a material parameter that reflects the polarity and
"shape" of the molecule, i.e., it is different for every molecule and therefore must be looked
up!
C!bic E#!ations of "tate
Another important class of equations of state is the cubic ones. !hey are called cubic
equations of state because, mathematically, the equations are third order polynomials or
cubic equations in . (Dote that the truncated virial equation is quadratic (ubic equations
are basically better than quadratic equations in estimating the relation among the physical
parameters. !he shape of the curve in the phase envelope can explain it. !he two most
important cubic equations of state are van der ?aals equation and 'oave-Cedlich-Iwong
('CI equation. Fan der ?ants equation is similar in form to 'CI.
&an der -aals E#!ation
Fan der ?aal@s equation is a second order approximation of the equation of state of a gas and
will wor/ even when the density of the gas is not low.

(f - $#
where a and b are constants particular to a given gas and can be rearranged to a form of
equation (*qn xx which is interesting to examine because it is easy to discuss qualitatively
the origin of its deviation from ideality.
(f - $$
'ymbols LbB and LaB are material dependent constants and can be calculated from a set of
material independent equations. !hey represent roughly the volume of the gas molecules (b
and the KinteractionK of the gas molecules (a. As usual, the constants are correlated to the
critical constants of the materials"
) - #-
(f - $-
(f - $.
!he ideal gas law, P& % n'TC can be derived by assuming that the molecules that ma/e up the
gas have negligible sizes, that their collisions among themselves and with the walls are
perfectly elastic, and that the molecules have no interactions with each other.
Table F ( 1. 'ome van der ?aals (onstants
Sub&'ance A
(M
.
m
-
4mole
b
(m
-
4mole
P
c
(J<a
T
c
(I
Air %.#-06 -.5.x#%
-0
-.88 #-- I
(arbon ;ioxide ((N
$
%.-5.- ..$8x#%
-0
8.-: -%..$ I
Ditrogen (D
$
%.#-5# -.60x#%
-0
-.-: #$5.$ I
9ydrogen (9
$
%.%$.8 $.50x#%
-0
#.-% --.$ I
?ater (9
$
N %.00%8 -.%.x#%
-0
$$.%: 5.8.- I
Ammonia (D9
-
%..$-- -.8-x#%
-0
##.$6 .%5 I
9elium (9e %.%%-.# $.-.x#%
-0
%.$- 0.$ I
)reon (((l
$
)
$
#.%86 :.:6x#%
-0
..#$ -60 I
!he parameter b is related to the size of each molecule. !he volume that the molecules have
to move around in is not +ust the volume of the container V, but is reduced to (V 4 nb.
!he parameter LaB is related to intermolecular attractive force between the molecules, and
n.V is the density of molecules. !he net effect of the intermolecular attractive force is to
reduce the pressure for a given volume and temperature.
?hen the density of the gas is low (i.e., when n.V is small and nb is small compared to V the
van der ?aals equation reduces to that of the ideal gas law.
Nne region where the van der ?aals equation wor/s well is when the temperatures are
slightly above the critical temperature T
c
of a substance.
) - #.
Figu$e F ( 17 TITLE
Nbserve that inert gases li/e helium have a low value of a as one would expect since such
gases do not interact very strongly, and that large molecules li/e freon have large values of b.
!here are many more equations of state that are even better approximation of real gases.
F.*.,. Co"#$e&&ibili'% Fac'o$ an3 Co$$e&#on3ing S'a'e&
A simpler (mathematical way of representing non-ideality is through compressibility
factor
+,&3n-" or (f - $0
DEFINITION
!he co"#$e&&ibili'% <ac'o$, z, is a dimensionless number that represents a material@s
deviation from ideal gas behavior. !he gas equation using z results to a linear expression,
which is very simple to use. 9owever, obtaining the value of z is not that simple. 9owever,
charts are available for the generalized compressibility factor, z, as a function of the reduced
temperature and pressure.
The "law" at corresponding states suggests that gases behave similarly depending on how
far they are from their critical points. Thus, it can be deduced that if we use the reduced
temperature and pressure instead of the actual T and P, all gases will behave similarly. In the
case of Hydrogen and Helium it is necessary to add 8K and 8 atm to the critical temperature
and pressure, respectively, to make them behave like a "corresponding states" material.
&f ! or < is not given, use instead and the corresponding ideal Kreduced volumeK"
) - #0
(f - $5
OBJECTIVES:
Use one (or even all) of the covered non-ideal equations (SRK,
compressibility factor, van der Waals, virial equation) to determine P, V, or T
F.*.D. @on4I3eal =a& Mix'u$e&
&t is unclear how one would use any of the above expressions for mixtures because we
have material-dependent quantities li/e , 2, a, b, etc. 9owever, empirical (experience-
based rules have been developed and we will discuss the one for the compressibility
factor.
DEFINITION
Suggested Approach. Use pseudo-critical properties to calculate pseudo-reduced
quantities that are then used in the generalized compressibility charts. That is
T'
c
= y
A
T
cA
+y
B
T
cB
+... (f - 27)
P'
c
= y
A
P
cA
+y
B
P
cB
+... (f - 28)
(f - 29)
=sing the same procedure as in single-component systems, you can then get the pseudo-
reduced quantities and obtain the (generalized compressibility factor off a chart.
F.!. LIEFIDS
Aiquids are mobile and have the ability to move around, to change their shapes to conform to
that of the container, to flow in response to pressure difference (gradient, and to displace
another substance or ob+ect. Aiquids occupy a ixed volume and possess a definite surace,
though it cannot be discounted that the surface is visible due to the large difference in density
between the liquid and the space above it. !his observable surface is actually the reflection
and refraction of light as it passes through the boundary between the two phases with different
densities /nown as the index o reraction.
Aiquid is considered by most as the preferred state of any substance at temperatures
intermediate between the realms of solid and gas. 9owever, the temperature difference
between the melting and boiling points of many compounds the temperature range at which
) - #5
most substances can exist as liquid is small compared to solids and gases. !his ma/es
liquids somewhat perilous and tenuous, as if liquids have little or no right at all to exist.
'ubstance )ormula
Jelting
<t.
(I
2oiling
<t.
(I
Fiscosity
(centipoise
'urface
!ension
(dynes4cm
2enzene (
5
9
5
$86.50 -0-.#0 %.50$ $6.:
Deon De $..0 $8.# 0.0
?ater 9
$
N $8-.#0 -8-.#0 # 8-
)ructose (9
$
N9((9N9
-
(N(9
$
N9 :0-#%0

'olid and liquid volumes are also responsive to temperature and pressure, but the response is
quite little compared to that of gases and can usually be ignored.
F.!.1. Flo; P$o#e$'ie& o< LiAui3&
Aiquids occupy a somewhat unfamiliar place in the holy trinity of phases solid, liquid and
gas. !heir molecules are in contact similar to those of solids> but the ability of these liquid
molecules to slip and slide or loosely move around each other gives liquid the ability of a gas.
!his ability, however, is more beneficial than detrimental from the chemistry point of view
ma/ing liquid the favored state in chemical reactions. )avored reaction condition is where
molecules are in intimate contact but quite mobile. !he property is highly desirable in fast
reactions where there is a rapid chemical change among the reacting species and the
generation of products and by-products. !his condition enables close contact between the
reacting species and at the same time allows the reactants and product to move about freely so
that more contacts are established.
F.!.*. Vi&co&i'%
&t is easy to notice the relative ease at which water, vinegar, honey, and liquid detergents pour
out of their containers compared to catsup and mayonnaise. !he difference is due to the
viscosity of the substance.
,iscosity is defined as a measure of the resistance to flow, which is related to the strength of
the forces acting on the molecular units. 9oney, for example, is a concentrated solution of
fructose molecules. )ructose has the molecular formula 9N(9
$
((9N9
-
(N(9
$
N9. !his
compound contains five hydroxyl groups (-N9 that are capable of forming multiple
hydrogen bonds with water and with each other. !hese molecular interactions (physical
reaction draw molecules closer, thus hindering the movement of fructose and water
molecules resulting to stic/y disordered networ/ of these molecules. !o reduce this effect (or
shall we say to pour the liquid easily warming helps. ?arming the syrup increases the
) - #8
/inetic energy of the molecules ma/ing them more mobile, which wea/ens or even disrupts
hydrogen bond formation due to thermal agitation. Another example is lubricating oils, which
consist of long-chain hydrocarbon molecules that interact through dispersion forces. !he
interaction of long hydrocarbon molecules could result to molecular entanglement.
!he dependence of the viscosity of liquids (fluids in general on temperature has been
observed in daily activities and has been /nown even in early times. *dible and automotive
oils are viscous at low temperatures.
Fiscosity impedes motion or flow. &t is noticeable that when a syrup is poured out of the
container different parts of the fluid move at different rates and at times in different
directions. !he intermolecular attractive forces restrain molecules from pulling away from
their immediate neighbors and attaching themselves to new molecules. A fluid can move
freely only if its particles are able to flow independently.
!he pressure drop observed when a liquid flows through a pipe is the result of viscosity. !he
explanation for this is that intermolecular forces greatly influence the molecules right next to
the walls> these molecules tend to adhere to the walls, which hinders their movement. !his
layer of molecules then holds bac/ and impedes the movement of the next layer. !he effect is
transmitted inward towards the center of the pipe. !his is called the viscous drag effect and is
proportional to pressure drop. !he viscous drag effect normally decreases towards the center
of the tube.
!hese attractive forces depend on the nature of the walls and the moving fluid. 'mooth
surfaces li/e those of tubes made of plastics have wea/ attractive forces towards water and
some organic solvents. 9owever, metal pipes and even glasses have relatively high attractive
forces to water and solutions of electrolytes.
F.!.!. Su$<ace Ten&ion
'urface tension is created through the attraction of the molecules in liquids to each
other. &f one views a molecule at the interior of a medium, it would be equally attracted to all
neighboring molecules. !he effect is that it is attracted to all sides with the same force, so that
) - #6
Figu$e F ( 11. TITLE
the resulting force is zero (see )igure. Nn the other hand, if a molecule is located at the
surface of a liquid, the attraction from the interior of the medium wor/s further on one side,
whereas there are no more molecules on the other side. 9ence the resulting force is directed
towards the interior of the liquid. Nn the microscopic scale this causes drops of liquid to be
round since the surface of the liquid is minimized that way. !herefore surface tension, O is
defined as the energy, w needed to stretch or increase the surface area, A of the liquid and we
write
d$
dw

!he unit of surface tension is energy per unit area say +oules per sq. meter (M4m
$
. Eenerally,
values of O are reported in newtons per meter (Dm
-#
since #M= #Dm or dynes per cm.
Capillary action

!he upward movement of a liquid in a narrow tube against the force of gravity, which is
called capillary action is a consequence of surface tension> such is also responsible for the
shape of the meniscus curved surface in a capillary tube.
!he force f
#
(downward pull exerted by a column of liquid of height, h is
gh r f
$
#

where
is the density of the liquid, r is the radius of the capillary and g is the acceleration
due to gravity. !he force f
$
(upward pull due to surface tension is
r f $
$

At equilibrium f
#
=f
$
, hence the surface tension is equal to
grh
$
#
(#
!his simple expression (eq.# provides a reasonably accurate way of measuring the surface
tension of liquids by capillary rise method when the contact angle is negligible.
F.-. SOLFTIO@S
) - #:
'olutions are homogeneous mixtures of two or more components" the solutes and the
solvent(s. !he solvent is the substance in greater amount and usually but not necessarily a
liquid. ?ater is the most common among the usual solvents used. 'olutions in which water
is the solvent are called aqueous solutions. !he solute is the substance in lesser amount.
A mixture is defined as the combination of different substances where each substance retains
its chemical properties. Eenerally, mixtures can be separated by non-chemical means such as
filtration, heating, centrifugation or distillation.
Jost chemical reactions that are carried out in industries, laboratories and living organisms
ta/e place in solution. 'olutions provide a convenient and accurate means of introducing
/nown small amounts of a substance to a reaction system, e.g. titration.
A mixture is homogeneous when all particles exist as individual molecules or ions. A
homogeneous mixture is uniform throughout such that two same-size samples, one from the
bottom and the other from the top, are identical. 9omogeneous mixtures do not settle out if
left undisturbed, whereas a heterogeneous mixture would. 2lood is an example of a
heterogeneous mixture. 'ome homogeneous mixtures have particle size that is much larger
than individual molecules. 9owever, the particle size is so small that the mixture never settles
out. (olloid, sol, and gel are examples of mixtures.
(oncentration refers to how much solute is dissolved in solution. ;ilute means that only a
little solute is dissolved and concentrated means a lot is dissolved. !here are two common
concentrations used that are numerical in nature" molarity and molality.
Jolarity of a solution is determined by calculating the number of moles of solute per liter of
solution.
(f - -#
!o dilute a solution, means to add more solvent without the addition of more solute.
Assuming that volume is additive, the following formula is applicable"
moles before dilution = moles after dilution
4
1
,
1
& 4
2
,
2
(f - -$
!he subscript L#K refers to the situation before dilution while the subscript L$K refers to after
dilution, though the subscript is immaterial.
) - $%
Jolality of a solution is determined by calculating the number of moles of solute per
/ilogram of solvent.
(f - --
"ol!bility
!he general dividing line between soluble and insoluble is %.#J at $0G(. !hus, any
substance that can form %.# J or more is soluble otherwise it is insoluble. !his value was
pic/ed with a purpose. !here are e. substances that have their maximum solubility close to
%.# J. Almost every substance of any importance in chemistry is either much more soluble
or much less soluble. &n the past, some would have a third category slightly soluble.
Solubili'% $ule& 'ha' a##l% 'o ;a'e$ &olu'ion&0
#. All al/ali metals (lithium, sodium, potassium, rubidium, and cesium and
ammonium compounds are soluble.
$. All acetates, perchlorates, chlorates, and nitrates compounds are soluble.
-. 'ilver, lead, and mercury(& compounds are insoluble.
.. (hlorides, bromides, and iodides are soluble.
0. (arbonates, hydroxides, oxides, phosphates, silicates, and sulfides are
insoluble. 'ulfates are soluble except for calcium and barium.
!hese rules are to be applied in the order given. )or example, <b'N
.
is insoluble because rule
$ comes before rule 0. &n li/e manner, Ag(l is insoluble because rule $ (the smaller ta/es
precedence over rule - (the larger.
F.8. COLLI=ATIVE PROPERTIES
Nftentimes solutions are described in terms of the concentration of one or more solutes.
9owever, there are other physical properties of the solution that depend more directly on the
solvent concentration such as vapor pressure, boiling point, freezing point and osmotic
pressure. !hese four properties are tied together and referred to as the colligative properties
of solutions. (olligative properties of the solution explain the escaping tendency of the
solvent molecules in the presence of non-volatile solute. 'ince it is dependent on the amount
of solvent, it can be written also as a function of the amount of solute in the solution but not
the /ind or nature of the solute particles in the solution.
) - $#
!he escaping tendency of the solvent in the presence of a solute depends in part on how much
disorder the solute can create on the solvent. !his is also similar to the escaping tendency of
the solute. 2asically it is based on how much disorder is created when two or more
substances are mixed. *vaporation for instance creates a large disturbance due to the greater
volume occupied by the vapor as compared to the liquid. &f the liquid solvent is diluted in the
presence of the non-volatile solute, the increase in disorder in entering the vapor phase is less
(Caoult,s Aaw. !he vapor pressure of the solvent can be linearly expressed as shown in the
equation below.
p & +
o
x (f - -.
where +
o
and PxP are the vapor pressure and mole fraction of the pure solvent,
respectively.
!he vapor pressure lowering is defined as the difference between +
o
and p" + & +
o
5p. )or
dilute solutions, this can be presented as a function of the amount solute preset in the solution
as shown below"
p
solvent
&+
o
solvent
015x
solute
1 (f - -0
+ & +
o
5p & +
o
solvent
x
solute
(f - -5
!his shows that the depression in vapor pressure is linearly dependent on mole fraction of
non-volatile solute.
!he lowering of vapor pressure increases the temperature to restore the vapor pressure to the
value corresponding to the pure solvent, in particular the boiling point. !hus, the lowering of
vapor pressure increases the boiling point of the pure solvent in the presence of non-volatile
solute. !he difference in boiling point or the boiling point rise is defined as !
b
= !-!
o
. !his
relation is quite complicated at a relatively high concentration of the solute due to
intermolecular interactions among and between solutes and solvents. 9owever, for relatively
dilute solutions this relation is linear and can be derived using the (lausius-(lapeyron
equation. (oiling point elevation is when the solution boils at a temperature above the boiling
point of the pure solvent at a given pressure. )or dilute solutions, the following relation
holds"
"
b
& "5"
o
& 6
b
m (f - -8
?here !
o
is the normal boiling point of pure solvent, I
b
is the ebulloscopic constant and m is
molality of the solution.
!he freezing point is the temperature at which the solid and liquid can simultaneously coexist
which means the escaping tendency of the molecules from the two phases is the same.
) - $$
'imilarly, ree3ing point depression is when the solution freezes at a temperature below that
of the pure solvent.
7smosis is the net movement of the solvent in the direction opposite to the diffusion of the
solute. !ypically it involves the use of a semipermeable membrane (membrane that allows
only the solute to transfer from one side of the membrane. Nsmosis is an important
biological function and if forced to run in reverse (8reverse osmosis8 becomes an important
technology for production of fresh water from seawater.
Jany pure liquids, and even some solids, evaporate to a slight extent at almost any
temperature producing a slight gas pressure above the surface. &magine what happens when
you introduce some pure liquid water into a rigid-walled container that is empty (in vacuum.
<art of the liquid evaporates into gas and after some time a state, /nown as e*uilibrium, is
established between the gas and the liquid. !he pressure exerted by the gas is called vapor
pressure, which is measurable. Fapor pressure is dependent on temperature only. &n a
solution, say sugar in water, the vapor pressure of the solution is lower than that of the pure
solvent at the same temperature. !his lowering in vapor pressure is used commercially in
what is /nown as vapor pressure osmometry for molecular weight determination. Also,
boiling point elevation is a direct result of vapor pressure lowering.
F.8.1. O&"o'ic P$e&&u$e
Nsmotic pressure is also a colligative property. !he greater the concentration of the solution,
the more pressure is needed to stop the solvent equalization process, and thus the greater the
osmotic pressure.
Dote that the solvent passed through the semipermeable membrane from the pure solvent to
the solution, as nature tries to equalize the quantity of solvent per mA on both sides.
!he solution (left chamber will always have a non-zero mole fraction of solute, and therefore
will never have a solvent mole fraction of oneQ !he pure solvent, on the other hand, must have
a solute mole fraction of exactly zero, and a solvent mole fraction of exactly oneQ 'o, what
stops the process if equalization is never reachedR !he answer to this seeming paradox is that
) - $-
as the difference in the levels in the two open tubes increases, so does the pressure difference
exerted by the atmosphere. ?hen the pressure difference exerted on the surfaces of the liquids
contained in the two tubes is +ust enough to stop the flow, that pressure difference is /nown as
the osmotic pressure/
!his pressure difference is easy to measure. 'imply measure the difference in heights in the
two tubes and convert that height to the equivalent height of mercury by multiplying by
density
solvent
4density
9g

97"%: !his conversion of pressure units is reasonably valid as long as the concentration of
the solution is low enough that the density of the solution is approximately the same as that of
the pure solvent.
!he amount of osmotic pressure exerted can be measured and explained via an easy equation,
which is discussed in the Nsmosis *quation file.
C-" (f - -6
F.8.*. 2oiling Poin' Ele5a'ion
A solution containing a non-volatile solute will boil at a temperature higher than that of the
pure solvent. !he more non-volatile solute is present in solution the greater is its effect. An
equation has been developed for this behavior.
" & 6
b
m (f - -:
!he boiling point temperature difference between the pure solvent and the solution is directly
proportional to the molality of the solute in solution. !he proportionality constant I
b
is
/nown as the ebullioscopic constant or molal boiling point constant (refer to the derivation of
6
b
in textboo/s. !able # presents the list of common solvents and their corresponding 6
b
values.
Table F ( *. 'ome (ommon 'olvents and (orresponding 6
b
Falues
'ubstance I
b
2enzene $.0-
(amphor 0.:0
(arbon tetrachloride 0.%-
*thyl ether $.%$
?ater %.0$
) - $.
!he unit of the constant is degrees (elsius per molal (G( mS
#
. !here are some variations
such as"
# I m
-#
- the distance between a single (elsius degree and a Ielvin are the same.
$ G( /g mol
-#
- this one ta/es molal (mol4/g and brings the /g.
!he last one is very useful because it splits out the mol unit. ?e will be using this equation
(or the freezing point to calculate molecular weights. Ieep in mind that the molecular
weight unit is grams 4 mol (molal, which is moles solute over /g solvent.
F.8.!. F$eeGing Poin' De#$e&&ion
A solution will solidify (freeze at a lower temperature than the pure solvent. !he more solute
in the solution the greater is the effect. An equation has been developed for this behavior. &t
is"
" & 6
m (f - .%
!he temperature change from the pure solvent to the solution is equal to two constants times
the molality of the solution. !he constant 6
is actually derived from several other constants

and its derivation is covered in textboo/s of introductory thermodynamics. 9ere are some
Kmolal freezing point depression constantsK"
Table F ( !. 'ome (ommon 'olvents and (orresponding 6
Falues
'ubstance I
f

benzene 0.#$
camphor .%
carbon tetrachloride -%.
ethyl ether #.8:
water #.65
!he unit discussion pertaining to 6
b
also applies to 6
/
F.8.-. 2oiling Poin' an3 F$eeGing Poin' o< Solu'ion&
<ure substances have true boiling points and freezing points, but solutions do not. )or
example, pure water has a boiling point of #%% G( and a freezing point of % G(. &n boiling for
) - $0
example, as pure water vapor leaves the liquid, only pure water is left behind. Dot so with a
solution.
As a solution boils, if the solute is non-volatile, only pure solvent enters the vapor phase. !he
solute stays behind (this is the meaning of non-volatile. 9owever, the consequence is that
the solution becomes more concentrated hence, its boiling point increases. &f you were to plot
the temperature change of a pure substance boiling versus time, the line would stay flat. ?ith
a solution, the line would tend to drift upward as the solution became more concentrated.
A non-volatile solute is one that stays in solution. !he vapor that boils away is the pure
solvent only. A volatile solute, on the other hand, boils away with the solvent.
'alt in water is an example of a non-volatile solute. Nnly water will boil away and, when dry,
a white solid (Da(l remains. 9exane dissolved in pentane is an example of a volatile solute.
!he vapor will be a hexane-pentane mixture. 9owever, here is something very interesting.
!he hexane-pentane percentages in the vapor will be dierent from the percentages of each in
the solution. ?e will get into that.
Nne last thing that deserves a small mention is the concept of an azeotrope. !his is a constant
boiling mixture. ?hat this means is that the mixture of the vapor coming from the boiling
solution is the same as the mixture of the solution. !he first occurrence was reported by
;alton in #6%$, but the word was not coined until #:##.
Nne example of a binary azeotrope is .1 (by weight water and :51 ethyl alcohol. ?hat this
means is that you cannot produce pure or #%%1 alcohol (called absolute alcohol by boiling.
Tou must use some other means to get the last .1 water out. &t also means that absolute
alcohol is hygroscopic, Hi.e., it absorbs water from the atmosphere.
!he #::$ 9andboo/ of (hemistry and <hysics lists the following"
Azeotrope Dumber
2inary #8.-
!ernary #88
Uuaternary $#
Uuinary $
9ere is the composition of one quinary system. &t boils at 85.0 G (
'ubstance
<ercent
by ?eight
?ater :..0
) - $5
Ditromethane -8.-%
!etrachloroethylene $#.#0
n-<ropyl alcohol #%.06
n-Nctane $#.0$
!he same lowering of the freezing point (sometimes called solidification also happens with
metal alloys such as solders. An alloy actually has a melting point below that of either of its
parent metals. !he ratio with the lowest point is called a KeutecticK alloy> a 5- parts tin to -8
parts lead electrical solder is one such eutectic mixture.
Immiscible Li#!ids
A mixture of two immiscible ideal liquids, say liquids A and 2 will exert their own vapor
pressure as if each one is present alone. &f the vapor pressures of the pure components are
o
B
o
$
P P C , then the total vapor pressure (+ is
o
B
o
$
P P P +
(f - .#
&f we consider
$
n
and
B
n
to be the moles of each component present in the vapor,
then the composition of the vapor expressed as mole ratio is
o
B
o
$
B
$
P
P
n
n
(f - .$
'ince the ratio of partial pressures is constant at a given temperature the ratio
B
$
n
n
must
also be constant. !hus the composition of the vapor (or distillate is constant as long as both
liquids are present.

!he fact that the total vapor pressure of the immiscible mixture is the sum of the pure
component,s vapor pressure (as shown in eq.# serves as the basis of the steam distillation
process. 'team distillation allows some heat-sensitive> water-insoluble oils and other organic
compounds to be distilled at a lower temperature than their normal boiling point. !he only
drawbac/ is that the distillate is in proportion to the vapor pressure of the components (see
equation $, so oils of low volatility distill in low abundance. !he moles of organic liquid
purified per mole of steam used maybe calculated using equation ($. &f the weight ratio in the
distillate is the desired then equation ($ is simplified to obtain
B
o
B
$
o
$
B
$
,- P
,- P
w
w
(f - .-
where
$
w
is the weight of the organic liquid in the distillate and
B
w
is the weight of water
or steam in the distillate.
$
,-
and
B
,-
are the molecular weights of components A and
2 respectively .
) - $8

0ernst Distrib!tion Law
&f a third substance is added to a two-phase liquid mixture, it distributes itself according to its
relative solubility in each phase. )or example, acetone is soluble in both water and chloroform
H two nearly immiscible liquids. &f a mixture of acetone and water is contacted with
chloroform, acetone distributes itself between the water and chloroform layers in such a way
that at equilibrium the ratio of the concentrations of acetone in the two layers is constant at
any given temperature.
'uppose A and 2 are immiscible liquids and a solute is distributed between the phases of an
A-2 mixture. !he partial molal free energy of the solute in liquid A,
$
is represented by

$
o
$
$
a 'T ln + (f - ..
and for liquid 2
B
o
B B
a 'T ln + (f - .0
where
o
B
o
$
and are the standard Eibbs free energies while a
A
and a
2
are the activities of
the solute in solvents A and 2, respectively. 'ince A and 2 are completely immiscible, two
layers will be formed. *ach layer contains the dissolved solute.
At equilibrium where ! and < are constant, the Eibbs free energy of the layers are equal, i.e.,
B $
. 9ence, *quations (# and $ are equal. *quating the two equations will result to
the simplified equation presented in *quation -.

B
$
a
a
ln

'T

o
$
o
B

(f - .5
9owever, at constant temperature,
o
B
o
$
C are constant for any given substance in the
particular solvents. 9ence

t cons
a
a
B
$
'an ln

1
a
a
B
$
ln
(f - .8
*quation (. is the mathematical statement of the Dernst distribution law, which states that at
equilibrium the ratio of the activities of the solute distributed between two phases is constant
at any given temperature.

) - $6
)or dilute solutions or when the solute behaves ideally, the activity of the solute is equal to its
concentration> hence, equation (. becomes

B
$
C
C
1
(f - .6

where the constant I is called the distribution or partition coefficient of the solute between
the two immiscible solvents. *quation 0 can be used only when the solute in both phases is
chemically the same, which means that no association, dissociation, or reaction with the
solvent ta/es place.
*xtraction is one of the most common analytical and industrial operations .&t refers to the
transfer of a compound from one phase to another phase, which are immiscible with each
other.
'uppose ;
o
grams of substance is dissolved in ,
#
mA of solution, and say this solution
is sha/en repeatedly with ,
$
mA samples of pure immiscible second solvent in n separate
extractions. &n each extraction, the solute is allowed to distribute in the two solvents until
equilibrium is attained. !he weight ;n of unextracted solute after n extractions will be
(f - .:
and the 1 of solute extracted (1* is
( )
#
1 #%% #
#
n
m
%
2
1
1

1
+
]
(f - 0%
where
#
$
&
&
1 D
m

.
F.6. SOLFTIO@S OF ELECTROLYTES
*lectrolytes are substances whose aqueous solutions conduct electric current. &t is the
presence of ions, which can move through the solution, that allow the conduction of
electricity. 'ometimes the ions are already there in the ionic salt, and at other times they result
from the reaction of the substance with the solvent. ?hen an ionic substance is bro/en apart
) - $:
n
o n
& 1&
1&
2 2

,
_
$ #
#
into solvated cations and anions, the process is called 3i&&ocia'ion, since the ions which are
already present in the salt simply separate or dissociate. 9owever, when the ions are formed
by the reaction of the substance with water and do not exist in the original substance, the
process is called ioniGa'ion. !he solution of potassium chloride and sodium hydroxide
illustrates dissociation of ionic solids by solvent molecules
I(l
(s
7 9
$
N V I
7
(aq
7 (l
-
(aq
DaN9(s 7 9
$
N V Da
7
(aq
7 N9
-
(aq
while the solution of acetic acid in water and of hydrogen chloride in liquid ammonia
illustrates ionization of neutral molecules
9(
$
9
-
N
$(l
7 9
$
N
(l
V 9
-
N
7
7 (
$
9
-
N
$
-
9(l(g 7 D9
-(l
V D9
.
7
7 (l
-

'olutions of electrolytes maybe classified as strong electrolytes or wea/ electrolytes. S'$ong
elec'$ol%'e& are substances, which are completely dissociated in water or substances for
which the ionization reaction goes to completion. &n other words, after the substance has
dissolved in water, the original substance no longer exists at any appreciable concentration.
!he types of substances which are typically classified as strong electrolytes are soluble salts
(e.g. Da(l, Jg(l
$
, strong inorganic acid (the common ones are hydrochloric acid,
hydrobromic acid, sulfuric acid, chloric acid and perchloric acid and strong inorganic bases
( e.g. DaN9. Hea9 elec'$ol%'e& only ionize partially in water and carries small amount of
electric current. !he types of substances, which behave as wea/ electrolyte are wea/
inorganic acids (e.g. carbonic acid, nitrous acid, hypochlorous acid, organic acids (carboxylic
acids e.g. acetic acid, ammonia and organic amines, e.g. methyl amine.
!o /now what happens when a strong electrolyte dissolves, lets consider A
x
2
y
as an example
of a strong electrolyte. )or complete ionization"
A
x
2
y
(s 7 9
$
N (l -----W xA
y7
(aq 7 y2
x-
(aq
*ach mole of A
x
2
y
dissolved generates x moles of cations and y moles of anions. )or
example, Da(l generates one mole of Da
7
ions and one mole of (l
-
ions or a total of $ moles
of ions while Al
$
('N
.
-
forms 0 ions.
'ince the colligative properties are linearly related to the number of non-volatile solute
present in the solution, it can be deduced that the dilution effect of the solvent also increases
in proportion to the increase in the number of solute. &n most cases, dissociations of
electrolytes are not complete. !hus the total number of ions in the solution is equal to the sum
) - -%
of cations, anions and the unionized salt present in the solution. !his leads to the van,t 9off
factor Li,, which is the ratio of the colligative properties of the ionized salt to those of the
unionized form. &n case of complete ionization, the factor is equal to the sum of x and y. )or
example, the freezing point of the electrolyte is equal to"
<"
& i6

m (f H 0#
i & "
=06
m
solute
1 & "
= "
o
(f - 0$
where "
o
is the freezing point depression calculated as though there were one particle per
mole of the solute.
!he last colligative property is the osmotic pressure. Nsmosis is the movement of solvent
molecules through a semipermeable membrane. !he spontaneous direction of osmosis is from
the region of low solute concentration to the region of high solute concentration. !his could
be called the Kprune principleK because this phenomenon is often seen when someone ta/es a
prune and put it in water before eating it. !he prune, shriveled as it loo/s, contains a little bit
of water and a relatively high concentration of sugar behind a semipermeable membrane (the
s/in of the prune. Nbserving the prune in the water, we see that osmosis of the water will
occur from the region of low solute concentration to the region of high solute concentration.
Nsmosis will continue until the prune s/in bursts from the increased pressure inside the prune.
!his increased pressure is called osmotic pressure because the reason for the increase in
pressure is osmosis. &t is always very important to understand what is the cause and what is
the effect in any process. !he osmotic pressure ( and the concentration of solute is given by
a limiting law shown below.
& c-" (f - 0-
Dote the similarity to the limiting gas law, + & n-"=, & c-". !he osmotic pressure generally
is rather large (e.g., the osmotic pressure of common seawater is about .8 atm> we can wor/
with very dilute solutions and still have a considerable osmotic pressure. ?or/ing at lower
concentrations means that the limiting law is more closely followed by experiment. 2ecause
osmotic pressure is very large, it is often used to determine the molecular weights of
un/nowns rather than freezing point depression.
Ceverse osmosis is used in countries near a body of salt water such as the ocean to remove the
salts from the water. !he salt water is forced through the semipermeable membrane to remove
the salts from the water. Ce-hydration of patients in hospitals is done with an isotonic (iso-
osmotic solution so that the solution does not cause an abnormal osmosis to occur in the
cells.
?e can calculate the ex#ec'e3 freezing point of a %.#%% molal aqueous solution of sodium
chloride using the following information"
) - -#
&an 't Hoff 3actor
!he van @t 9off factor, symbolized by the lower-case letter i, is a dimensionless constant
directly associated with the degree of dissociation of the solute in the solvent. 'ubstances
which do not ionize in solution such as sugar have i = #, while those that will completely
ionize into two ions such as Da(l have i = $ and into three ions such as Jg(l
$
, have i = - and
so on.
Colligati+e Properties of "ol!tions of Electrolytes
!he colligative properties of electrolyte solutions do not coincide with those of non-
electrolytes. !he disparity is caused by the dissociation of electrolytes into ions in solution,
which in turn increases the total number of particles in solution. !o account for this effect,
Fan,t 9off suggested the following modified equations"
$
0 iP P
o
(f - 0.
m i1 T
b b

(f - 00
m i1 T
f f

(f - 05
iC'T (f - 08

where i is /nown as the van,t 9off factor and is defined as follows"
solution in dissolved initially units formula of number
on dissociati after solution in particles of number actual
i
!he factor i is greater than one and it changes with concentration. )or strong electrolytes in
dilute solution, the Fan,t 9off factor is approximately equal to the total number of ions
yielded by a molecule of the electrolyte, thus for 9(l, Da(l, etc. i= $> for Da
$
'N
.
, 2a(l
$
etc.i
= -. 9owever, for wea/ electrolytes, the van,t 9off factor i involves the degree of the
dissociation. 'uppose one molecule of a wea/ electrolyte produces X ions when completely
dissociated. &f Y is the degree of dissociation, then the number of ions actually produced is YX,
and the number of molecules left undissociated is #-Y. !he number of particles produced from
one molecule is
i& 15> ) >? (f - 06
and therefore

#
#
i
(f - 0:
) - -$

)or wea/ electrolytes, the formula shown in equation 0 measures approximately the degree of
dissociation or ionization of ionic solutes in solvents of low dielectric constant and the degree
of ionization of covalent solutes. &t does not measure the degree of dissociation or ionization
of strong electrolytes because the ionic concentration is large such that inter-ionic effect
dominates.
Ionic "trength
!he ionic strength (Z of a solution is defined as

$
$
#
i
i
i
4 c

(f - 5%

where c
i
is the molar concentration and z
i
is the valence of the ions of type i/ !he ionic
strength of a solution may come from a single salt or a mixture of any number of salts. )or #-
# electrolytes li/e Da(l and IDN
-
the ionic strength is equal to the molarity but for other
types of electrolytes the two are not equal. )or example in a solution of Da
-
<N
.
(a #--
electrolyte of molarity c and assuming dissociation is complete, the concentration of the
univalent sodium ion is -c and that of the trivalent phosphate ion is c. Applying equation #,
ionic strength therefore of Da
-
<N
.
is 5c.

)or a solution containing two or more non-reacting salts, the total ionic strength is +ust the
sum of the ionic strength of the individual salts.
,ean $cti+ity Coefficient
!he mean activity coefficient (
t
of a solution can be estimated using the equation below"

+ t
4 4 B
#%
log
(f - 5#
where 2 is a constant, z
7
and z
-
are the corresponding valence of the cation and anion,
respectively, and [ is the total ionic strength of the solution. *quation $ is /nown as the
;ebye-9uc/el limiting law. )or aqueous solution at $0
o
( equation $ becomes

+ t
4 4 0# %
#%
. log
(f - 5$
) - --
F.:. ELECTROCHEMICAL CELLS
#H
!he p9 of a solution is a measure of the molar concentration of hydrogen ions in the solution
and as such is a measure of the acidity or basicity of the solution. !he letters p9 stands for
Kpower of hydrogenK and the numerical value is defined as the negative base #% logarithm of
the molar concentration of hydrogen ions.
pH & 5log
10
@H
)
A (f - 5-
!he measurement of the p9 of a sample can be done by measuring the cell potential of that
sample in reference to a standard hydrogen electrode, as in the accepted procedure for
measuring standard electrode potentials. !his procedure would give a value of zero for a #
Jolar solution of 9
7
ions, so that it defines the zero of the p9 scale. !he cell potential for
any other value of 9
7
concentration can be obtained with the use of the 9ernst e*uation. )or
a solution at $0G( this gives
%
cell
& 50/0BC2 log
10
@H
)
A (f - 5.
or
pH & %
cell
=0/0BC2 (f - 50
)or this expression, a base change from the natural log to the base #% logarithm is made in the
Dernst equation. &n practice, the p9 is not usually measured this way because it requires
hydrogen gas at standard pressure, and the platinum electrode used in the standard hydrogen
electrode is easily fouled by the presence of other substances in the solution (*bbing.
)ortunately, other practical electrode configurations can be calibrated to read the 9
7
ion
concentration. Aaboratory p9 meters are often made with a glass electrode consisting of a
silver wire coated with silver chloride immersed in dilute hydrochloric acid. !he electrode
solution is separated from the solution to be measured by a thin glass membrane. !he
potential, which develops across that glass membrane, can be shown to be proportional to the
hydrogen ion concentrations on the two surfaces. &n the measuring instrument, a cell is made
with the other electrode being a mercury-mercury chloride electrode. !he cell potential is then
linearly proportional to the p9 and the meter can then be calibrated to read directly in p9.
) - -.

Figu$e -.-. (A !he p9 electrode. (C Dumerical *xamples of p9 ('hipman et al., DATE
!he usual range of p9 values encountered is between % and #., with % being the value for
concentrated hydrochloric acid (# J 9(l, 8 the value for pure water (neutral p9, and #.
being the value for concentrated sodium hydroxide (# J DaN9. &t is possible to get a p9 of
-# with #% J 9(l, but that is about a practical limit of acidity. At the other extreme, a #% J
solution of DaN9 would have a p9 of #0.
&n pure water, the molar concentration of 9
7
ions is #%
-8
J and the concentration of N9
-
ions
is also #%
-8
J. Actually, when loo/ed at in detail, it is more accurate to classify the
concentrations as those of \9
-
N]
7
and \N9]
-
. !he product of the positive and negative ion
concentrations is #%
-#.
in any aqueous solution at $0G(.
An important example of p9 is that of the blood. &ts nominal value of p9 = 8.. is regulated
very accurately by the body. &f the p9 of the blood gets outside the range 8.-0 to 8..0 the
results can be serious and even fatal.
&f you measure the p9 of tap water with a p9 meter, you may be surprised at how far from a
p9 of 8 it is because of dissolved substances in the water. ;istilled water is necessary to get a
p9 near 8.
Jeters for p9 measurements can give precise numerical values, but approximate values can
be obtained with various indicators. Ced and blue litmus paper has been one of the common
indicators. Ced litmus paper turns blue at a basic p9 of about 6, and blue litmus paper turns
red at an acid p9 of about 0. Deither changes color if the p9 is nearly neutral. Aitmus is an
organic compound derived from lichens.
) - -0
<henolphthalein is also a common indicator, being colorless in solution at p9 below 6 and
turning pin/ for p9 above 6.
,eas!rement of Ion Concentration
Jethods have been developed for the measurement of the concentrations of various /inds of
ions using the cell potentials of special electrochemical cells. &f you form a voltaic cell with
two different /inds of metal electrodes, you get a characteristic cell potential for standard
conditions where the electrolytes are at the standard # Jolar concentration. &f the ion
concentrations are different from # J, then there is a change in the cell potential described by
the 9ernst e*uation/ Jeasurement of that change is in essence a measure of the ion
concentration, and can be exploited for that purpose.
<erhaps the best /nown is the measurement o pH, which is a measurement of the 9
7
ion
concentration. Nther ion selective electrodes have been developed for the measurement of I
7
,
(a
7
, Jg
7
, D9
.
7
, etc. *bbing cites an example of a specialized electrode designed for
measuring the concentration of urea, a non-electrolyte. !o do this, an electrode sensitive to the
D9
.
7
concentration is coated with a gel containing urease, an enzyme, which catalyzes the
decomposition of urea, producing ammonium ions. !he measured D9
.
7
concentration can
then be calibrated in terms of the urea concentration in the solution.
Electrochemical Cells
A class of oxidation and reduction reactions is used to provide useful electrical energy in
batteries. A simple electrochemical cell can be made from copper and zinc metals with
solutions of their sulfate salts. ;uring the reaction, electrons can be transferred from zinc to
copper through an electrically conducting path as a useful electric current.
An electrochemical cell is created by placing metallic electrodes into an electrolyte where a
chemical reaction either utilizes or generates electrical current. *lectrochemical cells, which
generate an electric current, are called voltaic cells or galvanic cells, and common batteries
consist of one or more such cells. &n other electrochemical cells an externally supplied
electric current is used to drive a chemical reaction, which would otherwise not occur
spontaneously. 'uch cells are called electrolytic cells.
F.,. VOLTAIC CELLS
) - -5
An electrochemical cell, which produces external electric current flow, can be created using
any two different metals since metals differ in their tendency to lose electrons. 3inc more
readily loses electrons than copper, so placing zinc and copper metal in solutions of their salts
can cause electrons to flow through an external wire that leads from the zinc to the copper
As a zinc atom provides the electrons, it becomes a positive ion and goes into aqueous
solution, decreasing the mass of the zinc electrode. Nn the copper side, the two electrons
received allow it to convert a copper ion from solution into an uncharged copper atom, which
deposits on the copper electrode, increasing its mass. !he two reactions are typically written
3n(s -W 3n
$7
(aq 7 $e
-
(u
$7
(aq 7 $e
-
-W (u(s
!he letters in parentheses are +ust reminders that the zinc goes from a solid (s into a water
solution (aq and vice versa for the copper. &t is typical in the language of electrochemistry to
refer to these two processes as Khalf-reactionsK which occur at the two electrodes.
3n(s -W 3n
$7
(aq 7 $e
-
!he zinc Khalf-reactionK is classified as oxidation since it loses electrons. !he terminal at
which oxidation occurs is called the KanodeK. )or a battery, this is the negative terminal.
(u
$7
(aq 7 $e
-
-W (u(s
!he copper Khalf-reactionK is classified as reduction since it gains electrons. !he terminal at
which reduction occurs is called the KcathodeK. )or a battery, this is the positive terminal.
) - -8
)or the voltaic cell to continue producing an external electric current, there must be a
movement of the sulfate ions in solution from the right to the left to balance the electron flow
in the external circuit. !he metal ions themselves must be prevented from moving between
the electrodes, so some /ind of porous membrane or other mechanism must provide for the
selective movement of the negative ions in the electrolyte from right to left.
*nergy is required to force the electrons to move from the zinc to the copper electrode, and
the amount of energy per unit charge available from the voltaic cell is called the electromotive
force (emf of the cell. *nergy per unit charge is expressed in volts (# volt = #
+oule4coulomb.
(learly, to get energy from the cell, you must get more energy released from the oxidation of
the zinc than it ta/es to reduce the copper. !he cell can yield a finite amount of energy from
this process, which is limited by the amount of material available either in the electrolyte or in
the metal electrodes. )or example, if there were one mole of the sulfate ions ('N
.
$-
on the
copper side, then the process is limited to transferring two moles of electrons through the
external circuit. !he amount of electric charge contained in a mole of electrons is called the
)araday constant, and is equal to Avogadro,s number times the electron charge"
)araday constant = ! & 9
'
e = 5.%$$ x #%
$-
x #.5%$ x #%
-#:
= :5,.60 (oulombs4mole
!he energy yield from a voltaic cell is given by the cell voltage times the number of moles of
electrons transferred times the )araday constant.
*lectrical energy output = n!%
cell
(f - 55
!he cell emf %
cell
may be predicted from the standard electrode potentials for the two metals.
)or the zinc4copper cell under standard conditions, the calculated cell potential is #.# volts.
F.9. OPTICAL METHODS
Aambert-2eer or 2ouger-2eer Aaw are the two simple laws underlying colorimetric analysis.
!hey are based on the fact that the degree of absorption of light by an absorbing medium is a
function of the depth of the medium through which the light passes. !o put it simply, when a
ray of monochromatic light passes through an absorbing medium, its intensity decreases
exponentially as the length of the medium increases, i.e., expressed by the symbols below"
l k
#
#
"
@
%
#%
,
_
(f - 58
or
l k
#
#
@ log
%
#%

,
_
(f - 56
) - -6
2eer,s law is based on the fact that the extent of absorption of light by a solution of a colored
solute is a function of the concentration of the solution. &t states that the intensity of a ray of
monochromatic light decreases exponentially as the concentration of the absorbing medium
increases.

c k
#
#
"
K
%
#%
,
_
(f - 5:
or c k
#
#
K log
%
#%

,
_
(f - 8%
(ombining these two laws the Aambert-2eer or 2ouguer-2eer law is obtained and expressed
in symbols as

kcl
#
#
"

,
_
#%
%
(f - 8#
or
kcl
#
#
,
_
%
#%
log
(f - 8$
where"
#
0
= intensity of incident light (i.e., light entering a solution
# = intensity of transmitted light (i.e., light leaving a solution
c = concentration of the solution
l = length of absorbing layer
,
_
%
#
#
"
= transmittance of the solution (f - 8-
#%%! = percentage transmittance of the solution (f - 8.
,
_
%
#%
log
#
#
'
= absorbance, or optical density of the solution (f -80
2eer,s law applies to monochromatic light and holds true only when changes in concentration
are not accompanied by changes in degree of ionization, association, dissociation, or solvation
of the solute. (onversely, the degree of divergence from the law can be used as a means of
) - -:
studying these phenomena quantitatively. &t follows from the Aambert-2eer law that if light
of the same intensity enters two solutions (A and 2 and ad+ustments of depths are made so
that the emerging beams are of the same intensity, then the transmission are the same, and
( ( ' '
l c l c
F.D.1. Colo$i"e'$%
(olorimetry is a useful quantitative method using the concept of 2eer,s law. &t is used for
measuring the quantity of a colored constituent by measuring the relative amount of
absorption of light passing through a solution of the constituent. (omparison can be made
directly or indirectly by either visual or electrical means, between the intensity of light
passing through the solution and the intensity of light of the same wavelength passing through
the solution (or series of solutions of the same substance, termed us the standard solutions or
reference solutions.
!here are several ways where colorimetry can be applied depending on the nature of the
substance or its capability to form colored derivatives or compounds. (# &tself is colored
thus, can be determined directly, e.g. permanganate ion. ($ Allowed to react with another
substance to form a colored compound, e.g. copper after reaction with ammonia to form deep
blue complex ions. (- =sed to displace an equilibrium existing between two colored
compounds and thus give a definite, determinable, intermediate shade of color to the solution,
e.g., determination of the p9 value of a solution from the color produced by the addition of an
indicator. !his method is limited to relatively low concentrations where it is reasonable to
assume linearity of the absorbance.
F.D.* S#ec'$o#ho'o"e'$%
'pectrophotometry is a colometric method using filter photometer or spectrophotometer. &t
measures the relative amount of light transmitted by an absorbing medium. &ts principal
difference lies in the fact that instead of ma/ing the measurement at the particular
wavelengths passed by a color filter in the system, it ma/es the measurement at any desired,
and easily controlled, range of wavelengths.
&n effect, the light from the source (e.g. incandescent lamp is divided into its spectrum
components by means of either a prism or a diffraction grating. !he desired region or band is
selected by moving the prism or grating to appropriately control the slits in the system. !he
narrower the slit, the more nearly monochromatic is the beam but the less is the intensity of
the light. &n general, slits are as narrow as is consistent for accurate readings. !he resulting
light over any controlled narrow range of wavelengths is passed through the absorption cell,
and the diminution in intensity is measured as in the case of most of the colorimetric methods
described before. !he intensity of measurements can be made visually but are more
accurately made by photoelectric devices. A curve can then be plotted to show the
relationship between the wavelength and either percent extinction or transmittancy. !he
result is often characteristic of a given substance and can be used to identify the constituents.
) - .%
F.D.!. Pola$i"e'$%
&n light waves the vibrations are wholly at right angles to the ray direction, and however
complicated these vibrations are at right angles to each other. (ertain crystals (e.g.,
tourmaline have the property of transmitting vibrations in a single plane and absorbing the
others. !he light emerging from such crystal is called polarized light. &f the polarized light is
passed through a second crystal held at right angles to the first, all the light is absorbed.
'olutions of those organic substances possessing one or more asymmetric carbon atoms (e.g.,
the natural carbohydrates have the power to rotate the plane of polarized light to a certain
extent. !o an absorber loo/ing toward the light source, some rotations are cloc/wise
(dextrorotatory, while others are countercloc/wise (levorotatory. &f a solution of such a
substance is inserted between the above two polarizing crystals, the plane of the light
emerging from the first crystal (the polarizer is rotated to some extent and the second crystal
(the analyzer has to be turned through an angle in order to cut out the light again. !his angle
depends on the wavelength of the light, the temperature of the solution, the nature of the
solute, the depth of the solution, and the concentration of the solution. 2y /eeping the other
factors constant, the angle through which the analyzer must be turned is therefore a measure
of the concentration of the solution. ;ifferent substances have different characteristic angles.
F.D.-. Re<$ac'o$% an3 In'e$<e$o"e'$%
Another optical property of a liquid that is occasionally useful in analytical wor/ is the
refractive index. !his is determined using a refractometer.. !he Abbe refractometer, which
requires only a drop or two of the sample, and the immersion refractometer are the two most
used instruments. !he determination of refractive index is useful in identifying oils, fats, and
organic liquids, and for ma/ing quantitative determinations in certain solutions and liquid
mixtures. ?ith careful control of temperature a precision of %.%01 can be expected.
Cefractive index can also be determined with much greater sensitivity by means of an
interferometer. !his instrument measures the difference in refraction of two liquids or gases.
!he measurement ma/es use of the fact that the light from a common source and traveling the
same distance in two separate beams will arrive at any point in phase, but if one path is
through a medium of higher refractive index, the two beams will be out of phase and show
interference bands. !he extent to which a compensator plate must be removed in the system in
order to bring the beams into phase is a measure of the refractive index. A precision of $ ppm
is obtainable.

Daniel Cell
*nglish chemist Mohn )rederic/ ;aniel developed a voltaic cell in #6-5 that used zinc and
copper and solutions of their ions.
) - .#
F.17. 2ATTERIES
2atteries use a chemical reaction to do wor/ on charge and produce a voltage between their
output terminals. !he basic element is called an electrochemical cell, which ma/es use of an
oxidation4reduction reaction. An electrochemical cell, which produces an external current, is
called a voltaic cell. Foltages generated by such cells have historically been referred to as emf
(electromotive force.
F.17.1. Ca$bon4/inc 2a''e$ie&
) - .$
!he carbon-zinc cell or Aechlanche@s
cell was invented in #655. &t was the
most common small battery
throughout most of the $%th century
until largely supplanted by al/aline
cells. !he oxidation at the zinc
electrode (the anode is
straightforward and similar to that in
other cells li/e the ;aniel cell. !he
other reactions involve JnN
$
, which
is contained near the carbon center
rod, and the D9
.
(l and 3n(l
$
which
ma/e up the bul/ of the paste
between the cathode and anode.
!he chemical reactions in this cell may be approximated by
3n(s -W 3n
$7
(aq 7 $e
-
Anode
$D9
.
7
(aq 7 $JnN
$
(s 7 $e
-
-W Jn
$
N
-
(s 7 9
$
N(l 7 $D9
-
(aq
(athode
'ome of the complexities of this reaction come from the fact that the reduction of the
ammonium ion produces two gaseous products
$D9
.
7
(aq 7 $e
-
-W $D9
-
(g 7 9
$
(g
that must be absorbed to prevent the buildup of gas pressure. !hat is accomplished with two
further reactions in the paste electrolyte. 3inc chloride reacts with ammonia to form solid
zinc ammonium chloride and manganese dioxide reacts with hydrogen to form solid
dimanganese trioxide plus water (9ewitt.
3n(l
$
(aq 7 $D9
-
(g -W 3n(D9
-
$
(l
$
(s
$JnN
$
(s 7 9
$
(g -W Jn
$
N
-
(s 7 9
$
N(l
!he voltage of this cell is initially about #.0 volts, but decreases as energy is ta/en from the
cell. &t also has a short shelf life and deteriorates rapidly in cold weather. Nxidation of the
zinc wall eventually causes the contents to lea/ out, hence such batteries should not be left in
electric equipment for long periods. ?hile these batteries have a long history of usefulness,
they are declining in application since some of their problems are overcome in al/aline
batteries.
) - .-
F.17.*. Al9aline D$% Cell&
Al/aline cells have solved some of the problems encountered in carbon-zinc batteries through
the use of potassium hydroxide in place of ammonium chloride in the electrolyte. <otassium
hydroxide is a base or al/aline material, hence the name Kal/alineK batteries. !he half-
reactions are
3n(s 7 $N9
-
(aq -W 3n(N9
$
(s 7 $e
-
Anode
$JnN
$
(s 7 9
$
N(l 7 $e
-
-W Jn
$
N
-
(s 7 $N9
-
(aq
(athode
!hese cells have much longer shelf life and perform better under drain and in cold weather.
!hey avoid the use of the zinc-corroding ammonium ions and do not produce any gaseous
products.
F.17.!. Lea34Aci3 2a''e$%
) - ..
F.17.-. Lea34Aci3 2a''e$%
!he reaction of lead and lead oxide with the sulfuric acid electrolyte produces a voltage.
'upplying energy and external resistance discharge the battery.
F.11. ELECTRIC POTE@TIAL E@ER=Y
<otential energy can be defined as the capacity for doing wor/, which arises from position or
configuration. &n the electrical case, a charge will exert a force on any other charge and
potential energy will arise from any collection of charges. )or example, if a positive charge U
) - .0
is fixed at some point in space, any other positive charge, which is brought close to it will
experience a repulsive force and will therefore have potential energy. !he potential energy of
a test charge q in the vicinity of this source charge will be"
where / is (oulomb,s constant.
&n electricity, it is usually more convenient to use the
electric potential energy per unit charge called
electric potential or voltage.
F.11.1. S'an3a$3 Elec'$o3e Po'en'ial&
&n an electrochemical cell, an electric potential is created between two dissimilar metals. !his
potential is a measure of the energy per unit charge, which is available from the
oxidation4reduction reactions to drive the reaction. &t is customary to visualize the cell
reaction in terms of two half-reactions, an oxidation half-reaction and a reduction half-
reaction.
Ceduced species -W oxidized species 7 ne
-
Nxidation at anode

Nxidized species 7 ne
-
-W reduced species
Ceduction at cathode

!he cell potential (often called the electromotive force or emf has a contribution from the
anode, which is a measure of its ability to lose electrons - it is referred to as its Koxidation
potentialK. !he cathode has a contribution based on its ability to gain electrons - its
Kreduction potentialK. !he cell potential can then be written as
*
cell
= oxidation potential 7 reduction potential
&f we could tabulate the oxidation and reduction potentials of all available electrodes, then we
could predict the cell potentials of voltaic cells created from any pair of electrodes. Actually,
tabulating one or the other is sufficient, since the oxidation potential of a half-reaction is the
negative of the reduction potential for the reverse of that reaction. 9owever, two main hurdles
must be overcome to establish such tabulation. !hese are
#. !he electrode potential cannot be determined in isolation, but in a reaction with some
other electrodes.
$. !he electrode potential depends upon the concentrations of the substances,
temperature, and pressure in the case of a gas electrode.
&n practice, the first of these hurdles is overcome by measuring the potentials with respect to a
standard hydrogen electrode. &t is the nature of electric potential that the zero of the potential
) - .5
is arbitrary. &t is the difference in potential that has practical consequence. !abulating all
electrode potentials with respect to the same standard electrode provides a practical wor/ing
framewor/ for a wide range of calculations and predictions. !he standard hydrogen electrode
is assigned a potential of zero volts.
!he second hurdle is overcome by choosing standard thermodynamic conditions for the
measurement of the potentials. !he standard electrode potentials are customarily determined
at solute concentrations of # Jolar, gas pressures of # atmosphere, and standard temperature,
which is usually $0G(. !he standard cell potential is written with a degree sign as a
superscript.
!he example below shows some of the extreme values for standard cell potentials.
(athode (Ceduction
9alf-Ceaction
'tandard <otential
*
G
(volts
Ai
7
(aq 7 e
-
-W Ai(s --.%.
I
7
(aq 7 e
-
-W I(s -$.:$
(a
$7
(aq 7 $e
-
-W (a(s -$.85
Da
7
(aq 7 e
-
-W Da(s -$.8#
3n
$7
(aq 7 $e
-
-W 3n(s -%.85
(u
$7
(aq 7 $e
-
-W (u(s %.-.
N
-
(g 7 $9
7
(aq 7 $e
-
-W N
$
(g 7 9
$
N(l $.%8
)
$
(g 7 $e
-
-W $)
-
(aq $.68
!he values in the table are reduction potentials, so lithium at the top of the list has the most
negative number indicating that it is the strongest reducing agent. !he strongest oxidizing
agent is fluorine with the largest positive number for standard electrode potential. !he lin/
below ta/es you to a more extensive table.
S'an3a$3 Elec'$o3e Po'en'ial& in AAueou& Solu'ion a' *8IC
(athode (Ceduction
9alf-Ceaction
'tandard <otential
*
G
(volts
Ai
7
(aq 7 e
-
-W Ai(s --.%.
I
7
(aq 7 e
-
-W I(s -$.:$
(a
$7
(aq 7 $e
-
-W (a(s -$.85
Da
7
(aq 7 e
-
-W Da(s -$.8#
) - .8
Jg
$7
(aq 7 $e
-
-W Jg(s -$.-6
Al
-7
(aq 7 -e
-
-W Al(s -#.55
$9
$
N(l 7 $e
-
-W 9
$
(g 7 $N9
-
(aq -%.6-
3n
$7
(aq 7 $e
-
-W 3n(s -%.85
(r
-7
(aq 7 -e
-
-W (r(s -%.8.
)e
$7
(aq 7 $e
-
-W )e(s -%..#
(d
$7
(aq 7 $e
-
-W (d(s -%..%
Di
$7
(aq 7 $e
-
-W Di(s -%.$-
'n
$7
(aq 7 $e
-
-W 'n(s -%.#.
<b
$7
(aq 7 $e
-
-W <b(s -%.#-
)e
-7
(aq 7 -e
-
-W )e(s -%.%.
$9
7
(aq 7 $e
-
-W 9
$
(g %.%%
'n
.7
(aq 7 $e
-
-W 'n
$7
(aq %.#0
(u
$7
(aq 7 e
-
-W (u
7
(aq %.#5
(lN
.
-
(aq 7 9
$
N(l 7 $e
-
-W (lN
-
-
(aq 7 $N9
-
(aq %.#8
Ag(l(s 7 e
-
-W Ag(s 7 (l
-
(aq %.$$
(u
$7
(aq 7 $e
-
-W (u(s %.-.
(lN
-
-
(aq 7 9
$
N(l 7 $e
-
-W (lN
$
-
(aq 7 $N9
-
(aq %.-0
&N
-
(aq 7 9
$
N(l 7 $e
-
-W &
-
(aq 7 $N9
-
(aq %..:
(u
7
(aq 7 e
-
-W (u(s %.0$
&
$
(s 7 $e
-
-W $&
-
(aq %.0.
(lN
$
-
(aq 7 9
$
N(l 7 $e
-
-W (lN
-
(aq 7 $N9
-
(aq %.0:
)e
-7
(aq 7 e
-
-W )e
$7
(aq %.88
9g
$
$7
(aq 7 $e
-
-W $9g(l %.6%
Ag
7
(aq 7 e
-
-W Ag(s %.6%
9g
$7
(aq 7 $e
-
-W 9g(l %.60
(lN
-
(aq 7 9
$
N(l 7 $e
-
-W (l
-
(aq 7 $N9
-
(aq %.:%
$9g
$7
(aq 7 $e
-
-W 9g
$
$7
(aq %.:%
DN
-
-
(aq 7 .9
7
(aq 7 -e
-
-W DN(g 7 $9
$
N(l %.:5
2r
$
(l 7 $e
-
-W $2r
-
(aq #.%8
) - .6
N
$
(g 7 .9
7
(aq 7 .e
-
-W $9
$
N(l #.$-
(r
$
N
8
$-
(aq 7 #.9
7
(aq 7 5e
-
-W $(r
-7
(aq 7 89
$
N(l #.--
(l
$
(g 7 $e
-
-W $(l
-
(aq #.-5
(e
.7
(aq 7 e
-
-W (e
-7
(aq #...
JnN
.
-
(aq 7 69
7
(aq 7 0e
-
-W Jn
$7
(aq 7 .9
$
N(l #..:
9
$
N
$
(aq 7 $9
7
(aq 7 $e
-
-W $9
$
N(l #.86
(o
-7
(aq 7 e
-
-W (o
$7
(aq #.6$
'
$
N
6
$-
(aq 7 $e
-
-W $'N
.
$-
(aq $.%#
N
-
(g 7 $9
7
(aq 7 $e
-
-W N
$
(g 7 9
$
N(l $.%8
)
$
(g 7 $e
-
-W $)
-
(aq $.68
Calcula'ion o< Vol'aic Cell Po'en'ial&
?hen an electrochemical cell is arranged with the two half-reactions separated but connected
by an electrically conducting path, a voltaic cell is created. !he maximum voltage that can be
produced between the poles of the cell is determined by the standard electrode potentials
under the standard conditions under which those potentials are defined.
(onsider the historic ;aniel cell in which zinc and copper were used as electrodes. !he data
from the table of standard electrode potentials are"
(athode (Ceduction
9alf-Ceaction
'tandard <otential
*
G
(volts
3n
$7
(aq 7 $e
-
-W 3n(s -%.85
(u
$7
(aq 7 $e
-
-W (u(s %.-.
!he cell potential can be written as
*
cell
= oxidation potential 7 reduction potential
'ince the tabulated standard electrode potentials are reduction potentials, the one with the
most negative potential needs to be reversed in sign to get its oxidation potential. ?hen that
is done, it is clear that the theoretical standard cell potential for the zinc-copper cell is #.#%
volts.
) - .:
&n general, a real voltaic cell will differ from the standard cell, so we need to be able to ad+ust
the calculated cell potential to account for the differences. !his can be done through the
application of the Dernst *quation.
<resuming that there are two metal electrodes with their ions, the standard potential for a cell
with anode potential and cathode potential is the of the *
G
cell
. &f the ion concentration at the
anode is \A] molar and the concentration at the cathode is \(] molar, then the thermodynamic
reaction quotient U = \A]4\(]. )or temperature in I and number of electrons exchanged is the
calculated cell potential *
cell
. Dumerically exploring the above calculation, it can be
confirmed that large concentration differences between the anions and cations can cause the
voltage to differ significantly from the standard cell potential, and that such large
concentration differences also ma/e the cell potential more temperature dependent.
'ince the electrolysis process results in an increase in entropy, the environment KhelpsK the
process by contributing the amount !;'. !he utility of the Eibbs free energy is that it tells
you what amount of energy in other forms must be supplied to get the process to proceed.
Co$$o&ion A& An Elec'$oche"ical P$oce&&
(onsidering the s/etch of a water droplet (after *bbing in the figure below, the oxidizing
iron supplies electrons at the edge of the droplet to reduce oxygen from the air. !he iron
surface inside the droplet acts as the anode for the process
)e(s -W 7 )e
$7
(aq 7 $e
-
!he electrons can move through the metallic iron to the outside of the droplet where
N
$
(g 7 $9
$
N(l 7 .e
-
-W .N9
-
(aq
?ithin the droplet, hydroxide ions can move inward to react with iron(&& ions moving from
the oxidation region. &ron(&& hydroxide is precipitated.
)e
$7
(aq 7 $N9
-
(aq -W )e(N9
$
(s
) - 0%
Cust is then quic/ly produced by the oxidation of the precipitate.
.)e(N9
$
(s 7 N
$
(g -W $)e
$
N
-
^9
$
N(s 7 $9
$
N(l
Custing of unprotected iron in the presence of air and water is then inevitable because it is
driven by an electrochemical process. 9owever, other electrochemical processes can offer
some protection against corrosion. Jagnesium rods can be used to protect underground steel
pipes by a process called cathodic protection.
Ca'ho3ic P$o'ec'ion Again&' Co$$o&ion
=nderground steel pipes offer the strength to transport fluids at high pressures, but they are
vulnerable to corrosion driven by electrochemical processes. A measure of protection can be
offered by driving a magnesium rod into the ground near the pipe and providing an electrical
connection to the pipe. 'ince magnesium has a standard potential of -$.-6 volts compared to
) - 0#
-..# volts for iron, it can act as the anode of a voltaic cell with the steel pipe acting as the
cathode. ?ith damp soil serving as the electrolyte, a small current can flow in the wire
connected to the pipe. !he magnesium rod will be eventually consumed by the reaction
Jg(s -W 7 Jg
$7
(aq 7 $e
-
while the steel pipe as the cathode will be protected by the reaction
N
$
(g 7 $9
$
N(l 7 .e
-
-W .N9
-
(aq.
F.1*. ELECTROLYTIC CELLS
An electrolytic cell is an electrochemical cell in which the energy from an applied voltage is
used to drive an otherwise non-spontaneous reaction. !his type of cell can be produced by
applying a reverse voltage to a voltaic cell, li/e the ;aniel cell.
&f a voltage greater than #.#% volts is applied as illustrated to a cell under standard conditions,
then the reaction
(u(s 7 3n
$7
(aq -W 3n(s 7 (u
$7
(aq
will be driven by removing (u from the copper electrode and plating zinc on the zinc
electrode.
) - 0$
*lectrolytic processes are very important in the preparation of pure substances li/e aluminum
and chlorine.
F$ee Ene$g% an3 Elec'$o3e Po'en'ial&
!he cell potential of a voltaic cell is a measure of the maximum amount of energy per unit
charge, which is available to do wor/ when charge is transferred through an external circuit.
!his maximum wor/ is equal to the change in Eibbs free energy, ;E, in the reaction. !hese
relationships can be expressed as
Jaximum wor/ = D & 5n!%
E
cell
where n is the number of electrons transferred per mole and ) is the )araday constant.
(onsider the historic ;aniel cell in which zinc and copper were used as electrodes. !he data
from the !able of 'tandard *lectrode <otentials are
(athode (Ceduction
9alf-Ceaction
'tandard <otential
*
G
(volts
3n
$7
(aq 7 $e
-
-W 3n(s -%.85
(u
$7
(aq 7 $e
-
-W (u(s %.-.
!he standard cell potential is then *
G
cell
= #.# volt and $ electrons are transferred per mole of
reactant. !he change in free energy is then
E = -n)*
G
cell
= -$ x :5,.60 coul4mole x #.#% +oule4coul = -$#$ /M
!his relationship with free energy can be used in the opposite direction as well. )rom a "able
o "hermodynamic Fuantities, the free energy changes for the ions under standard conditions
are
3n
$7
(aq, ;E = -#.8.$# /M4mol
(u
$7
(aq, ;E = 5..:6 /M4mol
'ince 3n ion is produced and (u ion is reduced in the cell process, the net change in free
energy is -$#$ /M4mol, as we obtained above. 'tarting from these free energy changes, we
could have calculated the cell potential of #.# volts by reversing the above calculation.
Po'en'io"e'$ic Me'ho3&
) - 0-
Potentionmetric Titrations. ?e have seen how the emf of a voltaic cell is related to the
concentrations of the components of the cell. A potentiometric titration ma/es practical
application of this relationship. 2y setting up a cell in which the solution being titrated forms
one half-cell and a /nown and fixed equilibrium system forms the other half-cell, the
experimentally determined emf of the whole serves as a measure of the relative concentrations
of the constituents of the solution being titrated. <otentials are determined during the progress
of the titration, and when these values are plotted against buret readings, characteristic curves
are obtained that are of such nature as to ma/e possible the determination of the equivalence
point. <otentiometric methods are especially valuable in the titration of turbid or highly
colored solutions where the use of a chemical indicator is either unsatisfactory or impossible.
Calomel Cell/ !he most commonly used reference half-cell for potentiometric measurements
is the calomel cell (or calomel LelectrodeP and this is based on the half-cell equilibrium
( ) ( )

+ + Cl li*uid Hg s Cl Hg $ $ $
$ $

&t consists of metallic mercury in contact with a suspension of 9g
$
(l
$
(LcalomelP, which in
turn is in contact with a solution of I(l of definite concentration. ?ith reference to the
standard hydrogen electrode, and with our adopted sign convention, the electrode potential at
$0
%
( of the calomel half-cell is"
7%.$60 v , when # J I(l solution is sued
7%.--. v, when %.# J I(l solution is used
7 %.$.5 v, when saturated I(l solution is used.
All three concentrations are in common use, but to be consistent, we shall use only one molar
value. <ractically, the use of saturated I(l solution has the advantage that accidental loss of
water by evaporation does not cause a change in the salt concentration.
Potentionmeter acidimic of titrations/ ?e have seen how the hydrogen ion and p9 value of a
solution change during the process of an acidimetric or al/alimetric titration. !hese values
were calculated from combination and ionization concentration. &n a given titration, the type
of curve obtained from plotting these values against corresponding volumes of the titrating
solution were of help if the proper indicator is used.
&n potentiometric titration, the p9 values of the solution are experimentally determined using
the progress of the titration. 2y plotting the values against corresponding volumes of titrating
solution added, the concentration can be determined.
Hydrogen as Electrode/ &n an acidimetric titration, the calomel cell provides one of the half-
cells of the system. !he other half-cell is necessarily an electrode that is in equilibrium with
hydrogen ions. &n theory at least, the simplest electrode is the hydrogen gas electrode, which
is expressed by the simple half-cell equilibrium
) - 0.
( ) atm H H # $ $
$
+

+
5!inhydrone Electrode. &n actual practice, the hydrogen gas electrode is seldom used. &t
requires carefully prepared platinum blac/ and hydrogen gas of a high degree of purity, and it
is cumbersome to operate. !he quinhydrone electrode, on the other hand, consists merely of a
few crystals of an equimolar mixture of quinone and hydroquinone (made by pouring a hot
solution of ferric ammonium sulfate into a solution of ahydroquinone and recrystallizing the
precipitated crystals added directly to the solution to be titrated. A platinum wire and the
regular calomel cell are used as electrodes.
$ $ . 5 $ . 5
$ $ H 7 H C H 7 H C + +

+

(quinone (hydroquinone
An'i"on% elec'$o3e. 'everal metal-metal oxide electrodes can be used in acidimetric
measurements, but the most satisfactory one consists of metallic antimony coated with a
special crystalline form of antimonous oxide. Although several equilibria are involved, the net
equation
( ) ( ) 7 H s Sb H s 7 Sb
$ - $
- $ 5 5 + + +

+

shows the principal relationship.
lass electrode/ !he glass electrode is the one commonly used in modern p9 meters. &t
consists of a thin-walled bulb of special glass in which is sealed an electrode (usually silver-
silver chloride and 9(l solution. !he exact mechanism of this electrode is not entirely
understood, but hydrogen ions can apparently move in and out of the surface of the glass, and
the glass bulb thus seems to act li/e a semipermeable membrane between the reference
solution and the solution being tested. 2ecause of the high resistance of the glass bulb,
electronic amplification of the current is necessary. &n some forms this is offset by the facts
that (# there is no contamination of the solution being tested> ($ measurements can be made
on very small volumes of solution (by using small glass electrodes> and (- the presence of
oxidizing, reducing or complexing agents does not influence the results of a p9
determination.
2ecause of variations in composition of the glass used in the glass electrode, the formula for
determining the p9 value with a given electrode is usually provided by the manufacturer, but
slight changes can occur over long periods of time due to crystallization of the glass. &t is, of
course, possible to calibrate the electrode at any time against a prepared solution of /nown p9
value.
Jost modern portable p9 meters use glass electrodes and calomel cells in compact form and
are of such construction that p9 values can be read directly from the instrument. 2y means of
such a meter a p9 measurement can be made very quic/ly, and the manipulative technique
) - 00
involved is very simple. !itrations can be made almost as rapidly as by a chemical indicator
method.
Cond!ctance/ 'olutions of strong acids, strong bases, and most salts are good conductors of
the electric current and obey Nhm,s law (%&#-. !he resistance (- of a solution is expressed
in ohms> the conductance of a solution is the reciprocal of its resistance and is expressed in
reciprocal ohms (=ohms
-#
, or mhos.
) - 05

B400 Physical Chemistry

Uploaded by

Document Information

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

B400 Physical Chemistry

Uploaded by

Copyright:

Available Formats

Philippine Handbook Physical Chemistry

is actually derived from several other constants

of a solution can be estimated using the equation below"

You might also like