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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 and second law of
thermodynamics
3. Calculate the change in internal
energy
SCOPE
Thermochemistry
Chemical
Thermodynamics
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
Standard Heats of Reaction
3.1 Thermochemistry
All changes in matter - accompany by changes in
Thermodynamics:
the
study
of
heat
&
its
transformation.
Thermochemistry: branch of thermodynamics, deals
Energy
Forms of Energy and Their Inter
conversion
All
An object has:
energy:
E = q + w
(1)
Work done on
system
E = +ve
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) + 2HCl (aq) H2(g) + Zn2+ (aq) + 2Cl(aq)
As the H2 gas forms, the system used some of its
internal energy on the surroundings and push the
piston outward.
Energy is lost by the system as work, w = -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
SI unit = Joule (J)
1 cal (non SI unit) = 4.184 J
Heat, work, potential energy, kinetic energy are
expressed in Joules
In the case of work:
kgm
Work, w = Force (F) x distance (d)
2
s
where F = mass (m) x acceleration (a) in units of
2
kg
m
kg
m
w =
x m
J
2
2
s
s
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.
If the expanding gases do 451 J of work on
the pistons and the system loses 325 J to
the surroundings as heat, calculate the
change in energy (E) in J, kJ and kcal.
Solution
Define the system and surroundings
System - reactants and products
Surroundings - pistons, cooling system & rest of
the car
Heat released by the system, q = -ve, work
done by the system to push the piston outward,
w = -ve
Calculating E in J:
q = -325 J, w = -451 J,
E
=q+w
= -325 J + (-451J) = -776 J = -0.78 kJ
= -185.47 cal = 0.19 kcal
(1cal = 4.184
J)
system
E, P, V)
depend only on the initial and final states of the
system
are capitalized
3.1.2 Enthalpy
Enthalphy is a thermodynamic property of a
system.
Enthalpy is defined by H = E + PV
Thus, change in enthalphy, 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)
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,
V 0, PV 0, H E
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 +
PV
3.1.2 Enthalpy
Exothermic and Endothermic
Processes
Enthalphy is a state function
The enthalphy change of reaction, H, is
also called the heat of reaction, Hrxn.
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
Endothermic: Hfinal Hinitial, H 0/+ve
Example 1
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 H 0 and
the reaction is exothermic
(b) Heat is a reactant (on the left), so H 0 and the
reaction is endothermic
of
measured
T = quantity of
heat required to change the temperature of 1 gram
of a substance by 1K (Unit: J/g.K)
Example
A welded layer of copper on the bottom
of a skillet weighs 125 g. How much
heat
is
needed
to
raise
the
temperature of the copper layer from
250C to 3000C?
The specific heat capacity (c) of Cu is
0.387 J/gK.
Solution
T = Tfinal - Tinitial = 3000C - 250C = 2750C =
275 K
q = c x mass (g) x T
= 0.387 J/gK x 125 g x 275 K
= 1.33 x 104 J
Process:
solid (system) is
weighed, heated
to some known
temperature,
added to a
sample of water
(surroundings) of
known
temperature &
mass in the
calorimeter
heat
Final water temperature (final temperature of
Example
A 25.64 g sample of solid was heated in a
test tube to 100.000C in boiling water
and carefully added to a coffee-cup
calorimeter containing 50.00 g water.
The water temperature increased from
25.100C to 28.490C. What is the specific
heat capacity of the solid? (Assume all
the heat is gained by the water)
Solution
Plan -summarize the information
given.
J
4.184 x 50.00 g x 3.39 K
c H 2O x mass H 2O x TH 2O
gK
csolid
masssolid x Tsolid
25.64 g x (71.51 K)
J
0.387
gK
Constant-Volume Calorimetry
Common type: bomb
calorimeter
Use to measure very
precisely the heat
released in combustion
reaction
Known mass of the
sample and the heat
capacity of the
calorimeter, the
measured T is used to
calculate the heat
released
Example 4
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
by 4.9370C. Is the manufacturers claim
correct? (Heat capacity of the calorimeter
= 8.151 J/K)
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
= 40.24 J = 9.62
cal
(Hrxn)
Note: Hrxn value refers to the enthalphy change for
the amounts of substances in that specific reaction
(i) Sign
Sign of H depends on the reaction of the change
Sign of a forward reaction is opposite that of the
reverse reaction
e.g. Decomposition of 2 mol water (endothermic):
2H2O(l) 2H2(g) + O2(g)
Hrxn = 572
kJ
(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) H20(l)
Hrxn =
-286 kJ
Formation of 2 mol water
2H2(g) + O2(g) 2H2O
-572 kJ
Hrxn =
Calculating an unknown
H involves three
steps:
(i) identify the target equation, note the
number of moles of reactants and products.
(ii) manipulate the equations of known H - the
target numbers of moles of reactants and
products are on the correct sides
change the sign of H when reversing an
equation
multiply number of moles and H by the
same factor
(iii) Add the manipulated equations to obtain
the target equation. (cancel terms that appear
on both sides of equations). Add their H
Example 5
Application of Hesss Law:
to equation 3
identify eq. 3 as a target, carefully note the
number of moles of reactants and products
eq. 1 and 3 contain the same amount of S, so
leave eq. 1 unchanged
H1 =
H0f = -74.9
Example 6
Write balanced equations for the formation of 1 mole of the
following compounds from their elements in their standard states
and include H0f (To obtain values, refer to Table 6.5 - page 244,
Chemistry: the molecular nature of matter and change, 2nd Edition,
Silberberg)
(i) Silver chloride, AgCl, a solid at standard conditions
(ii)
Calcium carbonate, CaCO3, a solid at standard conditions
(iii)
Hydrogen cyanide, HCN, a gas at standard conditions
Solution
(i) Ag(s) + 1/2 Cl2(g) AgCl(s)
H0f = -127.1 kJ
(ii)
Ca(s) + C(graphite) + 3/2 O2(g) CaCO3 H0f = -1206.9 kJ
(iii) 1/2 H2(g) + C(graphite) + 1/2 N2(g) HCN (g) H0f = 135.1 kJ
(Products)
(Reactants)
Example 7
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) - mH0f
(reactants)
= {4H0f [NO(g)] + 6H0f [H2O(g)]}
{4H0f [NH3(g)] + 5H0f [O2(g)]}
= [4 mol (90. 3 kJ/mol) + 6 mol (-241.8
kJ/mol)]
[4 mol (-45.9 kJ/mol) + 5 mol (0 kJ/mol)]
= 361 kJ - 1451 kJ + 184 kJ - 0 kJ
Thermodynamics
The Molecular Interpretation of Entropy
Calculation of Entropy Changes
Gibbs Free Energy
Free Energy and Temperature
Free Energy and the Equilibrium Constant
Chemical
Thermodynamics
Area of chemistry that explores energy
relationship
sign of
products favoured
Chemical
Thermodynamics
Reactants or products favoured In addition
spontaneous process
related to disorder in chemical reaction
Spontaneous Process
Spontaneous process: Chemical or physical
Spontaneous Process
Temperature: have an impact on the
spontaneity
e.g. endothermic process of melting ice, at T
00C:
ice melts spontaneously
reverse process (liquid water ice), nonspontaneous
But at T 00C:
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
(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,
disorder
Entropy change,
S = Sfinal Sinitial
Molecular Interpretation of
Entropy
Structure & behaviour of molecules - affect the
gaseous molecules
generally leads to a decrease in entropy
Molecular Interpretation of
Entropy
e.g. 2NO(g) + O2(g) 2NO2(g)
entropy change = -ve because 3 molecules
Molecular Interpretation of
Entropy
Formation of the new bonds - decreases the
Molecular Interpretation of
Entropy
In general - entropy increases with increasing
temperature
when:
(i) Liquids or solutions are formed from solids
(ii) Gases are formed from either solids or
liquids
(iii) No. of molecules of gas increases during
a
chemical reaction
Calculation of Entropy
Change
Standard molar entropies, S0 - molar entropy
= sum of
n = amounts (mol) of the products
m= amounts (mol) of the reactants
Example 8
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 9
Choose the substance that has greater entropy in
each pair, and explain your choice:
(a) 1 mol of HCl(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
gases are more disordered than solids
(e) The sample containing 2 mol of HCl has twice the
entropy of the sample containing 1 mol
(f) The gaseous N2 sample has the higher entropy
because gases are more disordered than solids
Second Law of
Thermodynamics
Second Law of Thermodynamics: total energy of a
Second Law of
Thermodynamics
For a spontaneous process carried out at
a given temperature
The second law can be restated in a form
that refers only to the system
Consider the changes in entropy that
occur in the system
oprocess takes place entropy is
created, at the same time heat flows
into/out of the system
oentropy accompanies that heat flow
When heat flow into the system entropy
flows into the system
Second Law of
Thermodynamics
The change in entropy,
temperature:
S entropycreated
q
T
Second Law of
Thermodynamics
The restatement of the second law: for a
q
(equilibrium
process, Eq.1)
S
T
a phase change
e.g. Consider the melting of ice, Hfus 6.0 kJ (1 mol
of ice)
heat absorbed q
= heat of fusion, Hfus
S =
T
Hfus
S=
T
entropy change ,
Example 10
The heat vaporization, Hvap, of carbon tetrachloride,
CCl4, at 250C is 43.0 kJ/mol.
kJ/mol
CCl4(l) CCl4(g);
Hvap = 43.0
Solution
S =
H vap
T
J
43.0 10
J
mol
=
= 144
298 K
mol K
3
written?
If H & S for the reaction are known second law
q
=
in the S
form
can be used to answer the above
T
question.
qp H
The second law for aspontaneous
reaction at
S> =
T T
constant P:
H
S>
T
H
- S 0
T
H - TS 0 (-ve)
as written
reaction is spontaneous in the opposite direction
H - T S =0
reaction is at equilibrium
system, G = H - TS
G fo n G fo (products) m G fo (reactants)
= sum of, m = amounts (mol) of
reactants
n = amounts (mol) of products
Quantity of
Example 11
(a) Calculate the standard free-energy change for the
kJ
2 mol -16.66
mol
- 33.32kJ
kJ
kJ
H > magnitude of S
+ve enthalpy term dominates, leading to a +ve
value of G.
Melting of ice is not spontaneous at T < 00C,
reverse process (liquid water to ice) is
spontaneous at T < 00C
H
-ve entropy term dominates, leading to a negative
value of G
Melting of ice is spontaneous at T > 00C
Example 12
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
reaction
changes
with
increasing
temperature
(b) Calculate G0 for the reaction at 5000C
Solution
G0 become less negative (or more positive)
with increasing temperature.
Thus the
driving force for the production of NH3
becomes smaller with increasing temperature
G0 = H0 - T S0
- 92.38kJ 153kJ
61kJ
o
1kJ
3
10 kJ
The End