1.

Gases

Gas is one of the three states of mater

SI units for gases: pressure = N*m-2 = Pa (pascal), 1 bar = 105 Pa = 100kPa, 1atm =
101.33kPa =
a substance may exist in one or more states simultaneously (latent heat)
In a solid, the atoms, molecules, or ions are vibrating but locked in place (dimensional
stability)
o fixed position of particles in a lattice
o the stronger the interaction, the higher the MP/BP
o no translational motion, however the atoms or molecules possess vibrational
energy
o when the magnitude of vibrational modes overcomes the attractive forces, and the
atoms and molecules lose their fixed positions, the substance becomes a liquid
In liquids, the attraction b/w the atoms and molecules keeps them touching (still in lattice
but no dimensional stability)
if the atoms&molecules are completely free w/ significant translational energy, the
substance becomes a gas
pressure = collisions of gaseous particles with the walls of the container

Behaviour of Gases

certain boundaries made for studying gases:

o low pressure: atoms/molecules of the gas have negligible volume relative to a
container w/ low pressure
o high temperature: with higher temperature, we can ignore the effects of the gas
becoming liquid/solid at condensation/vaporization

Boyle

Charles

Boyle+Cha
rles

PV=const., PV=PfVf
V inversely proportional to P
fixed: moles of gas, temperature
use when only pressure and volume are changing

V/T=const.,

V directly proportional to T
fixed: moles of gas, pressure
use only when T and V are changing, temperature
MUST be in Kelvin

PV PfVf
=
T
Tf

V Vf
=
T Tf

use when moles constant and everything

changing

Avagadro

V Vf
=
n nf
equal volumes of different gases, at const.
temp and pressure, contain equal moles
V directly proportional to n
fixed: pressure and temperature
use to determine volume after mole change

PV = nRT, R=8.314 L*kPa*mol-1K-1 (match correct R val w/ units)

Molecular formula = (Emp. formula)*n
Challenge: pg1-13, q8 and 16 (starred)

1.2

d=

Ideal Gas Law

One mole of any ideal gas always occupies the same volume at const. temp. and pressure
equal volumes of different gases at the same temp. and pressure contain the
same moles
22.4L per 1 mol at STP (273.15K, 1atm) = molar volume of ideal gas

( MM ) P
dRT
MM =
RT
P
molar mass equal to durham regional transit over p

at const. temp. gas density is directly proportional to pressure

Daltons law of partial pressures: total pressures exerted by a mixture of gases is the
sum of all the partial pressures of these gases
o Pt = Pa + Pb + Pc
each gas exerts a partial pressure, this is the pressure the gas would exert if alone in the
container

X ind . gas =

nind .
n total

mole fraction =

at constant temperature and volume, the pressure is directly proportional to the

moles

ni P i
= =X i
nT PT

X a + X b + X c =1

Pi=X i PT

you can apply the ideal gas law to each individual constituent of a gas mixture
o PiV = niRT, volume and temp stay same, pressure and moles for indiv. gas
stopcock problem: calculate final partial pressures of individual constituents using
Boyles law, total volume of two containers for each PP.
% components of gas given: treat the % vals as X vals (mole fractions), use P=XPtotal
vapour pressure of liquid depends only on the temperature of the liquid
o depending on how hot it is, more of the liquid will be in gas phase
o boiling point is the temp. at which vapour pressure = atmospheric pressure
treat the vapour pressure of a liquid inside a container with Daltons law approach
o treat it as a partial pressure contributing to the entire pressure of the container

MM=
( X aMM a ) + ( X bMM b ) +(X cMM c )

remember, X is interchangeable w/ mole fractions and partial pressure fractions

density of a mixture w/ more than one gas: must determine the average molar mass

( MM

and use with dRT/p =MM eqn

Gas Rxn Stoichiometry

if everything else kept constant, we can use pressure or volume as if they were
moles in stoich
o multiply and transfer volumes just as you would moles with stoichiometric ratios

Kinetic Molecular Theory

assumptions:
o size of molecules is negligible when compared to space b/w them and volume of
container
o no vibrational or rotational energy (only translational/kinetic energy)
o elastic collisions w/ container and other molecules, momentum is conserved
o no attractive/repulsive forces b/w molecules
o avg. kin energy proportional to temp. in Kelvin

1
3 RT
PV = Nm u 2 , u 2 =
3
MM

inc. heat = inc. speed, const. temp = heavier molecules move slower

Maxwell
Boltzma
nn
distributi
on

area is constant for all curves

(equal moles for each
molecule type)
lighter molecules more
distributed
constant temperature

u rms ( A )
MM B
=
MM A
urms ( B )

effusion: flow of gas molecules at low pressures through tiny pores or pinholes
o lighter molecules effuse more rapidly than heavier ones (faster rms)
Grahams law: rate of effusion is inversely proportional to sq. root of MM

rate of effusion A N A
MM B
=
=
rate of effusion B N B
MM A

enrichment factor:
o

MM B
MM A

heavier MM must be (B)

if enrichment factor = y, then there are y as many B molecules as A

molecules

Challenge: pg1-34, 23, 24

2.1

Heat, Work, and Energy

Thermodynamics is the study of the energy changes involved in physical and
chemical processes
Thermochemistry is the branch of thermodynamics that investigates the heat flow
that occurs during these reactions
Heat is the transfer of thermal energy
o always flows from the warmer object to the cooler object when they contact
Sys. is the part of the universe one wants to study (open, closed, isolated)
Energy: is the capacity of a system to do work.
o energy can convert between heat energy, kinetic energy, potential energy, etc.
o q is the quantity of heat energy (J)
work defines as the [product of force acting on an object that causes the object to
displace
chemical work in form of pressure-volume (PV) work, the work involved in compression
or expansion of a gas
heat capacity heat energy associated with temperature changes
heat flow b/w two objects will occur till thermal equilibrium is reached

Specific heat
capacity (c)
Heat capacity (C)

q=mc T ,

JK-1

mass

q=C T ,

Jmol-1K1

objects
Molar heat
capacity (C)

q=nC T ,

Lol idk

moles

q always indicates the amount of heat transferred

if heat lost (q<0) exothermic, if heat gained (q>0) endothermic
o looking at the system of interest (delta T of reaction)
-q(warmer, loosing) = q(cooler, gaining)
T(final) is the same for both objects once thermal equilibrium is reached

intensive (intrinsic property) does not depend on the amount of material in the
system. (density, temperature)
extensive (extrinsic property) physical property is proportional to the size of the
system (volume, energy, entropy)
temperature is intensive as it measures the average kinetic energy of the molecules in the
system
thermal energy however, is extensive, at it measures the total kinetic energy of the
molecules in the system
o related to the amount of the sample, number of molecules increases thermal
energy.
o lake may have the same heat temperature as a cup of water, but the lake has way
more thermal energy
state function: properties whose values depend only on the current state of the system
(doesnt matter how the state was reached)
Heat and work are not state functions since the work done on or heat transferred to a
system by following different paths is different, although initial and final states could be
the same

First Law of Thermodynamics

The total energy of a system and surroundings is conserved

E, internal energy sum of all the kinetic and potential energies of all the atoms, ions,
and molecules in the sys.
o extensive and state fn
Abs. E cannot be determined, however change in internal energy can.

gas expansion means that the sys. does work on the surroundings (neg.)
gas compression means that the surroundings do work on the system (pos.)
w/o compression or expansion, change in volume = 0 therefore work is 0
Joule showed that heat and work are equivalent ways of transferring energy in/out of
system
E=q+w
o

If the surroundings do work on/supply heat to the system the internal energy of the sys.
increases
if the system is kept at constant volume, no expansion/compression work performed

2.2

E=qV

therefore at const. volume,

change in internal energy is all due to heat change with const. volume.

Enthalpy

Enthalpy (H): extensive, state property: energy content of a system at constant pressure
internal energy and enthalpy differ by pressure-volume PV done to or by the system

H= E+ P V
when breaking delta E into heat and work, work cancels out

at constant pressure,

Ho

means that the enthalpy change is under standard conditions (101.3kPA and

298.15K)
latent heat is the energy change associated with physical processes that involve a
change of phase
o temperature does not change, remains constant
o energy absorbed/given off to surroundings is only used to change the phase of the
substance
o Per gram or per mole
we cannot calculate the standard absolute enthalpy of anything, only change in it
Calorimeters are containers used to measure heat transfer, operating at constant
pressure
o qrxn = -Hcal
o in an endothermic rxn, the heat released by the system is absorbed by the
surroundings -> calorimeter + contents increase in temperature
o measure/given temp. change in calorimeter, if heat capacity is known, find the
enthalpy change in rxn
heat absorbed by the calorimeter itself considered negligible: Hwater = -Hrxn
calorimeter absorbs/releases heat, calibrate with water cooling
o qhot water = -qcal (heat lost by water must have transferred to the calorimeter)
o when determining qrxn, add (qsolution + qcal)
bomb calorimeters occur in const. volume, pressure changes made negligible through
over-pressurization
standard enthalpy of formation (Hof) enthalpy change occurring when one mole of a
substance is formed from its constituent elements in standard state
o constituents (standard state) -> 1 mole of a substance, H of of the substance
allotropy is the ability of an element to form different structures
standard enthalpy of formation for an element in its standard state = 0
o arbitrary reference point
Hesss Law: the enthalpy change for a reaction is the sum of the enthalpy changes for
the ind. steps of the rxn
o you can combine reaction enthalpies as enthalpy is a state function
o allows us to make statement that

H=q

H orxn= H of , products H of ,reactants

Bond Enthalpy: energy required to break one mole of a specific type of bond between
two atoms, provided the reactant and products are all in gaseous state
o formation = exothermic, breaking = endothermic
Total bond enthalpy: enthalpy of atomization, energy required to break all the bonds in
one mole of a gaseous compound
two methods to finding TBE of CH4:
1. CH4 (g) -> C (g) + 4 H (g) put rxn into this specific form then use eqn:
o
TBE= H rxn
= H of , products H of ,reactants

2. TBE = sum of all ind. bond energy

molecular structure features have a slight impact on bond enthalpy:
Bond strength increases with bond order (D bond > Single bond)
o not 2x energy!
if single reactant (in gas phase) involved in a reaction to constituents in gas phase (gas
phase rxn), we can use formula:

H may be used interchangeably as determined by enthalpies of formation and bond

enthalpies

2.3

Entropy and Spontaneous Change

spontaneous process: occurs w/o outside intervention

o heat transfer from hot object to cold object
o changes in enthalpy are insufficient to determine spontaneity
o doesnt necessarily equate to an eqn happening fast/slow
we must look at free energy: thermodynamic quantity that encompasses both enthalpy
and entropy
entropy (S): measure of disorder of a system.
o the higher the number of possible arrangements of a system, the greater the
entropy
entropy is a state function, therefore me measure a change in entropy
Pos. S means that entropy increased whereas neg. S means entropy decreased
What makes high entropy favorable?
o It is simply more probable
o The system with the largest number of possible arrangements is the most probable
Melting, sublimation, and vaporization increase entropy
count # of moles of gas on each side of eqn to see whether or not inc. or dec. in entropy
entropy due to vaporization >> entropy due to melting
entropy of a perfectly ordered crystalline solid at 0K is defined to be zero
o but at this state there is still zero-point energy caused vibrations
entropy increases with temperature (displacement)
o

S=

H
T

every spontaneous process increases the entropy of the universe

o overall change in entropy (system and surroundings) has to be positive
o universe in general tends towards disorder
standard molar entropies are assigned to elements and compounds
standard entropy change can be determined according to:
o

2.4

H rxn= BE broken BE formed

S = S products S reactants

Free Energy

every spontaneous process increases the entropy of the universe

Gibbs free energy is the amount of energy available or free to enable spontaneous
change to occur

o
o

G = H TS
state function

G= HT S

for a spontaneous reaction to occur,

G=0 at eq ' b

a neg. value for

G>0

G does not necessarily indicate that the rxn will proceed to

completion
o

rate of rxn is determined by chem. kinetics, thermodynamics has nothing to do with it

all systems tend towards lowest possible enthalpy and highest possible entropy
o with negative H (favorable) and S (unfavorable), or both positive H
(unfavorable) and S (favorable), the determining factor of the reaction running or
not is the temperature
o if the temperature is high enough it can offset a negative H
o if the temperature is low enough it can undermine a positive S
spontaneous processes with H << 0 and S < 0 are said to be enthalpically driven
spontaneous processes with H > 0 and S >> 0 are said to be entropically driven
(water evap.)
melting point temperature: temperature at which G=0 therefore H = TS (all
thermal energy used for phase change)
o similar for BP temperature
in standard conditions (1M, 101.3kPa, 298.15K) G = G o
Go, determine enthalpy and entropy changes using standard enthalpies/entropies of
formation and combine together

3.1

likewise, may proceed to a very small extent, even with positive

Equilibrium Constant

A system that is at equilibrium is dynamic and not static (forward and reverse rxns still
occur to a state where products and reactants are constant)
equilibrium: condition where the rate of forward rxn = rate of rev. rxn
for any eqb, there is a mathematical relationship b/w the pressures or conc. of the
reactants and products
o K
K is temperature dependent, whether the K value increases or decreases in response
to temp. change depends on whether the rxn is endo or exothermic
homogeneous eqb: all components in the same phase
K > 1 means the products are favored
K < 1 means the reactants are favored
reaction quotient (Q) indicates whether the sys. is at equilib, and the direction in which
the rxn must proceed to attain eqb
o system is at eqb when Q = K.
Q < K: less products, more reactants, must shift right
Q > K: more products, less reactants, must shift left

Conc. Change
Temp. Change
Pressure
Change

Shift away from side added to

Treat temp. like product/reactant
Shift to side with more moles (dec.
pressure b/c it inc. volume)

deltaG = 0 means that the system is at eqb, and the num. of moles of reactant and
product will not change over time
+G means the eqb lies to the left (reactants) and K is small
-G means that the eqb lies to the right (products) and K is large
Gof = -RT ln K to determine K value from standard gibbs free energy at 298.15K

ln K=

H S
+
RT
R , use to determine K from given delta H and delta S at temps other

than 298.15K

ln K

H
R

1
T

S
R

ln

Vant Hoff eqn gives the K values of a single reaction at varying temperatures

K2 H 1 1
=

K1
R T2 T2