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Chemical
Thermodynamics
LESSON OUTCOMES
At the end of this lecture, students
should be able to:
1. Recognize and use thermodynamic
terms: system, surrounding, heat,
work, internal energy, Gibbs Free
energy, enthalpy and entropy
2. Describe the first law and second law
of thermodynamics
3. Calculate the change in internal
energy
SCOPE
Thermochemistry
Chemical
Thermodynamics
3.1
Thermochemistry
Forms of Energy and Their
Interconversion
Enthalpy: Heats of Reaction and
Chemical Change
Calorimetry: Laboratory Measurement
of Heats of Reaction
Stoichiometry of Thermochemical
Equations
Hesss Law of Heat Summation
3.1.1
Energy
Forms
of Energy
and Their
Interconversion
All changes in matter - accompany by
changes in the energy/heat content of the
matter.
e.g. 1. Snow melts - energy is absorbed
2. H2O vapor condenses to rain energy is
release
Thermodynamics: the study of heat & its
transformation.
Thermochemistry:
branch
of
3.1.1 Energy
3.1.1 Energy
The System and Its
surroundings
System must be defined - to make a
meaningful observation &
measurement of a change in energy.
System: part of universe whose
change to be observed.
Surroundings: everything relevant to
the change of the system
The 3.1.1
system Energy
and Its
Surroundings
3.1.1 Energy
3.1.1 Energy
3.1.1
Energy
flow Energy
to and from
a system
Energy
Heat and3.1.1
Work: Two
Forms of
Energy Transfer
Energy transfer outward from the system or
inward from the surroundings can appear in
two forms; heat & work
Heat, q (or thermal energy)
energy transferred between a system and
its surroundings
as a result of a difference in temperatures
between the system and surroundings
Work, w
energy transferred when an object is moved
3.1.1
Energy
Heat and
Work: Two
Forms of
Energy Transfer
Total change in a systems internal energy:
E = q + w
q & w can be either +ve/-ve:
energy into the system: +ve
energy out from the system: -ve
3.1.1 Energy
3.1.1 Energy
Example of energy transfer as heat
only
E = -ve
Ice water in a beaker - Heat into a
system
System: ice water
q = +ve as heat was gained by the
3.1.1 Energy
Example of energy transfer as work only
Heat , q = 0. E = w
3.1.1 Energy
Example of energy transfer as work only
Work done by a system
Reaction between Zn & HCl in an insulated
container attached to a piston-cylinder assembly
System: atoms making up the substances
Zn (s) + 2H+ (aq) H2(g) + Zn2+ (aq) + 2Cl-(aq)
As the H2 gas forms, the system used some of the
internal energy on the surroundings and push the
piston outward.
Energy is lost by the system as work, w = -ve,
E = -ve
3.1.1 Energy
q = +ve : system gains heat
q = -ve: system loses energy
w = +ve: work done on system
w = -ve: work done by system
3.1.1 Energy
The Law of Energy Conservation /
The First Law of Thermodynamics
Energy
can be converted from one to another
cannot simply appear or disappear
cannot be created or destroyed
First Law of Thermodynamics: The total energy
of the universe is constant
3.1.1 Energy
The Law of Energy Conservation /
The First Law of Thermodynamics
Energy of the system + energy of the
surroundings remains constant: energy is
conserved.
A mathematical expression of the first law of
thermodynamics
3.1.1 Energy
Units of Energy
Example
When gasoline burns in a car engine, the heat
released causes the products CO2 and H2O
expand, which pushes the pistons outward.
Excess heat is removed by the cars cooling
system.
Solution
of the car
Heat released by the system, q = -ve, work
3.1.1
Energy
State Functions and the Path
Independence of the Energy
Change
Systems internal energy, E - state of
function
property determined by the current state of
the system
not dependent on the path the system took
to reach the state
Changes in state function (such as E, P,
V) depend only on the initial and final
states of the system
3.1.1
Energy
State Functions and the Path
Independence of the Energy
Change
Heat, q and work, w are not state function
their values depend on the path the
system takes in undergoing the energy
change
Note: Symbols for state functions (such as
E,P,V) are capitalized
3.1.2 Enthalpy
Enthalpy is a thermodynamic property of a
system.
Enthalpy is defined by H = E + PV
Thus, change in enthalpy, H = E + P V
(eq. 1)
Total change in a systems internal energy
under conditions of constant pressure,
E = qp + w
(eq. 2)
3.1.2 Enthalpy
In Chemistry, we are most often concern with
the reactions/systems that occur in solution
under conditions of constant atmospheric
pressure. Hence the system is free to expand
or contract and this means that it potentially
do work. Thus work done by the system, w =
P V (eq. 4)
Substituting eq. 4 in eq. 3,
H = qp (eq. 5)
Thus, the heat of reaction at constant
pressure is equal to H (change in
3.1.2 Enthalpy
Comparing E and H
For many reactions, H is equal / very close to E.
Three cases:
(i) Reactions that do not involve gases
e.g. 2KOH(aq) + H2SO4(aq) K2SO4(aq) +
2H2O(l)
Liquids & solids undergo very small volume
changes,
3.1.2 Enthalpy
Comparing E and H
(ii) Reactions in which the amount (mol) of gas
does not change. Total amount of gaseous
reactants = total amount of gaseous products
e.g. N2(g) + O2(g) 2NO(g), V = 0, PV = 0,
H E
(iii) Reactions in which the amount (mol) of gas
does change. PV 0, qp is usually much
larger than PV
From eq. 1, H = E + PV, H = qp = E +
P V
3.1.2 Enthalpy
3.1.2
Enthalpy
Exothermic and Endothermic
Processes
An exothermic (heat out)
process releases heat
results in a decrease in the enthalphy
Exothermic: Hfinal Hinitial, H 0/-ve
An endothermic (heat in)
process absorbs heat
results in an increase in the
enthalphy
Example
In each of the following cases, determine the
sign of H, state whether the reaction is
exothermic or endothermic
(a) H2(g) + 1/2 O2(g) H2O(l) + 285.8 kJ
(b) 40.7 kJ + H2O(l) H2O(g)
Solution
(a) Heat is a product (on the right), so
and
H 0
Enthalpy
Some 3.1.2
Important
Types of
Enthalpy Change
(i) Heat of combustion (Hcomb): when 1
mole of substance reacts with O2 in
a combustion reaction
e.g. C4H10(l) + 13/2 O2(g) 4CO2(g) + 5H2O, H =
Hcomb
3.1.2
Enthalpy
Some Important Types of
Enthalpy Change
(iii)Heat of fusion (Hfus): when 1 mole
of a substance melts
e.g. NaCl(s) NaCl(l), H = Hfus
(iv)Heat of vaporization (Hvap): when 1
mole of substance vaporize
3.1.3 Calorimetry
Measurement
of Heats of
Reaction
Enthalpy of a system in a given state
- cannot be measured
Change in enthalpy - can be measured
3.1.3 Calorimetry
Measurement
of Heats of
Reaction
Heat Capacity & Specific Heat
Capacity
Heat capacity, C = q/ T = quantity of
T =
quantity of heat required to change the
temperature of 1 gram of a substance
by 1K (Unit: J/g.K).
Example
Solution
T = Tfinal - Tinitial = 300oC 25oC = 275oC =
275 K
q = c x mass(g) x T = 0.387 J/gK x 125 g x
3.1.3 Calorimetry
3.1.3 Calorimetry
Constant-Pressure
Calorimetry
A coffee-cup
calorimeter
Process:
solid (system) is
weighed, heated to
some known
temperature, added to
a sample of water
(surroundings) of
known temperature &
mass in the calorimeter
3.1.3 Calorimetry
A coffee-cup
calorimeter
Continual
stirring which distribute the
released heat
Final water temperature (final temperature of
Example
A 25.64 g sample of solid was heated in a test
tube to 100.00oC in boiling water and carefully
added to a coffee-cup calorimeter containing
50.00 g water. The water temperature
increased from 25.10oC to 28.49oC. What is the
specific heat capacity of the solid? (Assume all
the heat is gained by the water)
Solution
J calculate c
Plan -summarize the information
given,
solidK
4.184
x 50.00 g x 3.93
c H 2 O x mass H 2O x TH 2O
gK
c solid =
=
masssolid x Tsolid
25.64 g x ( 71.51 K)
J
= 0.387
gK
3.1.3 Calorimetry
Constant-Volume Calorimetry
Common type: bomb
calorimeter
Use to measure very
precisely the heat
released in
combustion reaction
Knowing mass of the
sample and the heat
capacity of the
calorimeter, the
measured T is used
to calculate the heat
released
Example
A manufacturer claims that its new
dietetic dessert has fewer than 10
Calories per serving. To test the
claim, a chemist at the Department
of Consumers Affairs places one
serving in a bomb calorimeter and
burns it in O2. The temperature
increases 4.9370C. Is the
manufacturers claim correct?
Solution
When the dessert burns, the heat
released is gained by the
calorimeter:
-qsample = qcalorimeter
Heat is found by mutiplying the heat
capacity of the calorimeter by T
qcalorimeter = heat capacity x
T
= 8.151 J/k x
4.937 K
Thermochemical equations
a balanced equation that states the
heat of reaction (Hrxn)
Note: Hrxn value refers to the
enthalpy change for the amounts of
substances in that specific reaction
(ii) Magnitude
Magnitude of H is proportional to the
amount of substances in the reaction
e.g. Formation of 1 mol water:
H2(g) + 1/2 02(g) H2O(l) Hrxn =
-286 kJ
Formation of 2 mol water
2H2(g) + O2(g) 2H2O
Hrxn =
-576 kJ
Example
Application of Hesss Law:
Oxidation of sulfur trioxide
eq. 1: S(s) + O2(g) SO2(g)
-296.8 kJ
H1 =
H3 = ?
Solution
Manipulate eq.1 and/or 2 so that they add up
to eq.3
identify eq. 3 as a target, carefully note the
number of moles of reactants and products
Solution
(cont.)
Eq. 2 has twice as much SO3 as eq.3, so multiply
it by 1/2, multiply H2 by 1/2 as well
1/2(H2) =
-99.2 kJ
Eq. 3:
SO3(g)
S(s) + 3/2O2(g) SO3(g)
H0f =
Exampl
e
(iii)
Solution
(i) Ag(s) + 1/2 Cl2(g) AgCl(s)
H0f = -127.0 kJ
H0f = 135 kJ
e
Nitric acid, with an annual production of about 8 billion
kg, is used to make many products, including fertilizer,
dyes and explosive. The first step in its industrial
production is the oxidation of ammonia: 4NH3(g) +
5O2(g) 4NO(g) + 6H2O(g)
Calculate H0rxn from H0f values
Solution
H0rxn = mH0f (products) - nH0f (reactants)
= {4H0f [NO(g)] + 6H0f [H2O(g)]} - {4H0f
[NH3(g)] +
5H0f
[O2(g)]}
3.2 Chemical
Thermodynamics
Spontaneous Processes
Entropy
Molecular Interpretation of Entropy
Calculation of Entropy Changes
Second Law of Thermodynamics
Entropy Change for a Phase Transition
Gibbs Free Energy
Free Energy and Temperature
Free Energy and the Equilibrium Constant
3.2 Chemical
Thermodynamics
Area of chemistry that explores energy
relationship
Limitations of First Law of
Thermodynamics
only tells the amount of heat
released/work done by the system & the
amount of heat gained/work done on the
system
sign of H - not enough to predict
whether the reaction will proceed
3.2 Chemical
Thermodynamics
Reactants or products favoured In
addition to H, change in randomness
or disorder in chemical reaction is
considered
New aspect in discussion of
thermodynamics spontaneous
process
related to disorder in chemical
3.2.1 Spontaneous
Process
Spontaneous process: Chemical or
physical change occurs by itself
requires no continuing outside agency
/ occurs without any outside
intervention
A rock at the top of a hill
rolls down by itself - occur
spontaneously /
naturally
rolls up - not natural process /
3.2.1 Spontaneous
Process
Temperature: have an impact on the
spontaneity
e.g. endothermic process of melting ice,
at T 00C:
ice melts spontaneously (ice liquid water)
reverse process (liquid water ice),
nonspontaneous
But at T 00C:
liquid water converts into ice spontaneously
3.2.2 Entropy
Entropy, S
a thermodynamic quantity - a measure of
the randomness/disorder of a system.
SI unit: Joules per Kelvin (J/K)
a state function
quantity of S depends only on variables
(such as T & P) that determine the state of
substance
3.2.2
Entropy
Randomness/disorder of
the system
(i) Solids: have much more regular structure
than liquids.
Liquids > disordered than solids
(ii) Particles in a gaseous state are in random
motion.
Gases > disordered than liquids
(iii)Any process that increases the amount of
particles,
3.2.2
Entropy
Randomness/disorder of
the system
Consider the melting of ice:
Ice: an ordered crystalline structure
Ice melts liquid, crystalline structure
breaks down, resultant a less ordered
liquid structure
In ice, H2O molecules occupy regular, fixed
positions; ice has a relatively low S
In liquid water, molecules moves about
freely, disordered structure; liquid water has
greater entropy than ice
3.2.2
Entropy
Randomness/disorder of
the system
Entropy change, S
S = Sfinal Sinitial
S of a system to the disorder of the system
Ssystem 0,
implies the system becomes more
disordered
Ssystem 0,
Molecular Interpretation of
Entropy
In general - entropy increasing with increasing
temperature.
Entropy of the phases of a substance:
S = mS
products - n S reactants
o
= sum of
m = amounts (mol) of the products
n = amounts (mol) of the reactants
Example
Calculate S0 for the synthesis of ammonia
from N2(g) and H2(g):
N2(g) + 3H2(g) 2NH3(g)
Solution
S0 = 2S0(NH3) - [S0(N2) + 3S0(H2)]
Substituting the appropriate S0 values
J
J
J
S 2 mol 1925
1mol 191.5
3 mol 130.6
molK
molK
molK
J
-198.3
K
Example
Choose the substance that has greater entropy in
each pair, and explain your choice:
(a) 1 mol of NaCl(s) or 1 mol of HCl(g) at 250C
(b) 2 mol of HCl(g) or 1 mol of HCl(g) at 250C
(c) 1 mol of N2(s) at 24 K or 1 mol of N2(g) at 298 K
Solution
(d) Gaseous HCl has the higher entropy because
q
S entropycreated
T
q
the system is greater than the heat
T
q
S
T
equilibrium
process
Example
The heat vaporization, Hvap, of carbon
tetrachloride, CCl4, at 250C is 43.0 kJ/mol.
CCl4(l) CCl4(g)
Hvap = 43.0
kJ/mol
If 1 mol of liquid CCl4 at 250C has an entropy of
214 J/K, what is the entropy of 1 mol of the
vapor in equilibrium with the liquid at this
temperature?
Solution
1 mol of CCl4 increases in entropy by 144 J/K
when it vaporizes. Thus, entropy of 1 mol of
vapor = entropy of 1 mol of liquid (214 J/K) +
144 J/K = 358 J/mol.K
Hvap
S =
T
J
43.010
J
mol
=
=144
298K
molK
3
Energy
X J Willard Gibbs (1839 -1903) proposed a way to use H & S to
predict whether a given reaction will be
spontaneous
Gibbs proposed a new state function
Gibbs free energy (or just free energy)
Gibbs free energy, G = H - TS, T =
absolute temp.
At constant T, the change in free energy
of the system, G = H - TS
(i) If
G = +ve,
reaction in the forward reaction is
non spontaneous, work must be
supplied from the surroundings to
make it occur
reverse reaction will be spontaneous
(ii) If
o
G f (products)
o
G f (reactants )
= sum of,
m = amounts (mol) of products
n = amounts (mol) of reactants
Quantity of
reactants G0 > 0
Example
(a) Calculate the standard free-energy change for
reaction?
(a)
kJ
kJ
kJ
2 mol -16.66
1
mol
0
3
mol
0
mol
mol
mol
- 33.32kJ
G = H (enthalpy term) - T S
(entropy term)
Generally H & S change very little with
T. However, the value of T directly affects
the magnitude of -TS
As T increases, the magnitude of the term
-TS increases. It will become relatively
more important in determining the sign &
Example
The Haber process for the production of
ammonia involves the following equilibrium:
N2(g) + 3H2(g) 2NH3(g)
Assume that H0 and S0 for this reaction do
not change with temperature
(a) Predict the direction in which G0 for this
Solution
G0 become less negative (or more
- 92.38kJ 153kJ
61kJ
1kJ
3
K 10 kJ
value of
conditions
under
non-standard
standard conditions
Free-energy change under any other
conditions:
G = G0 + RT ln Q
R = ideal gas-constant, 8.314 J/mol-K
T = absolute temperature
Q = reaction quotient that corresponds to the
particular reaction mixture of interest
equation:
aA + bB pP + qQ
a, b, p & q = coefficients in balanced
chemical
p
q
equation (RECALL
CHEMISTRY
[ P] Q
I)equilibrium constant , K =
[ ]
[ A] [ B]
a
G
K exp
RT
The End