Chapters 29 and 35

Thermochemistry
and
Chemical Thermodynamics
1
Copyright (c) 2011 by Michael A. Janusa, PhD. All rights reserved.
 Thermochemistry
• Thermochemistry is the study of the energy effects that
accompany chemical reactions.

• Why do chemical reactions occur? What is the driving force of

rxn?
• Answer: Stability, wants to get to lower E. For a rxn to take
place spontaneously the products of reaction must be more
stable (lower E) than the starting reactants. Nonspontaneous
means never happen by self.
absorb E, nonspon
release E, spon
P
R

E P E R

lower E, more stable, less reactive 2

higher E, less stable, more reactive
 (

29.1 Reaction Enthalpy

• In chemical reactions, heat is often transferred from
the “system or reaction” to its “surroundings,” or vice
versa.
• system - the substance or mixture of substances
under study in which a change occurs.
• The surroundings are everything in the vicinity of
the thermodynamic system.


system or rxn + into system

- out system

surroundings
3
 Heat of Reaction
• Heat flow is defined as the energy that flows
into or out of a system. We follow heat flow
by watching the difference in temperature
between the system and its surroundings.
• Often we follow the surroundings temp
(solvent) and must realize that the opposite is
happening to the system. If system is
absorbing heat from the surroundings than
the temp of the surroundings must be
decreasing.
Tsystem (+) Tsurr (-)

4
 Heat of Reaction
• Heat flow or heat of reaction is denoted by the
symbol q and is the amount of heat required to return
a system to the given temperature at the completion
of the reaction.
 For an endothermic rxn the sign of q is positive;
heat is absorbed by the system from the
surroundings. Tsystem
Surroundings
absorb heat, nonspon (endo)
P
Tsurr
+q
E R
System

q > 0
5
 Heat of Reaction
 For an exothermic rxn, the sign of q is negative;
heat is evolved (released) by the system to the
surroundings.

Surroundings
Tsystem release heat, spon (exo)
R
-q E P
Tsurr
System

q < 0
6
 Enthalpy and Enthalpy Change
• The heat absorbed or evolved by a reaction
depends on the conditions under which it
occurs. ex. pressure
• Usually, a reaction takes place in an open
vessel, and therefore under the constant
pressure of the atmosphere.
• heat of this type of reaction is denoted qp; this
heat at constant pressure is named enthalpy and
given symbol H. H is the heat flow at constant
pressure.

7
 Enthalpy and Enthalpy Change
• Enthalpy, denoted H, is an extensive property of a
substance that can be used to obtain the heat
absorbed or evolved in a chemical reaction at
constant pressure.
– an extensive property - depends on the quantity of
substance.

– Enthalpy is a state function, a property of a system

that depends only on its present state and is
independent of any previous history of the system.

o o o

8
 Enthalpy and Enthalpy Change

• The reaction enthalpy for a reaction at a

given temperature and pressure

H  H (final)  H (initial )

H  H (products)  H ( reactants)

9
 Enthalpy and Enthalpy Change

• As we already stated the reaction enthalpy is equal to the heat

of reaction at constant pressure. This represents the entire change
in internal energy (U) minus any expansion “work” done by the
system; therefore we can define enthalpy and internal work by the
• 1st law of thermodynamics:
• In any process, the total change in energy of the system, U, is
equal to the sum of the heat absorbed, q, and the work, w, done by
the system.

• U = qp + w = H + w

10
– Changes in E manifest themselves as exchanges
of energy between the system and surroundings.
– These exchanges of energy are of two kinds; heat
and work - must account for both.
– Heat is energy that moves into or out of a system
because of a temperature difference between
system and surroundings.
– Work is the energy exchange that results when a
force F moves an object through a distance d;
work (w) = Fd
In chemical systems, work is defined as a change in
volume at a given pressure, that is:

w   PV
11
w   PV
negative sign is to keep sign correct in terms of system. For
expansion, V, will be a positive value but expansion involves
the system doing work on the surroundings and a decrease in
internal energy -- negative keeps it neg. For contraction work,
V, will be a negative value but contraction involves the
surroundings doing work on the system and an increase in
internal energy -- negative keeps it positive (- x - = +).
Giving us the 1st law of thermo is more useful form:

U  H  PV realize absorb heat (+)

release or evolved heat (-)
HW 44
code: first 12
 29.3 Thermochemical Equations
• A thermochemical equation is the chemical
equation for a reaction (including phase labels
{important}) in which the equation is given a molar
interpretation, and the enthalpy of reaction for these
molar amounts is written directly after the equation.

N 2 (g )  3H 2 (g )  2NH 3 (g ); H  -91.8 kJ
If H has a superscript like Ho, means thermo standard
conditions -- 25oC (298K) and 1 atm.

13
 Thermochemical Equations
• The following are two important rules for
manipulating thermochemical equations:
– 1.) When a thermochemical equation is
multiplied by any factor, the value of H for the
new equation is obtained by multiplying the H in
the original equation by that same factor.
2 H 2 ( g )  O2 ( g )  2 H 2O ( g ) ; H o  - 483.7 kJ
4 H 2 ( g )  2O2 ( g )  4 H 2O( g ) ; H o   967.4 kJ
– 2.) When a chemical equation is reversed, the
value of H is reversed in sign.
2 H 2 ( g )  O2 ( g )  2 H 2O ( g ) ; H o  - 483.7 kJ exo
2 H 2O( g )  2 H 2 ( g )  O2 ( g ) ; H o   483.7 kJ endo 14
 29.5 Hess’s Law
• Hess’s law of heat summation states
that for a chemical equation that can be
written as the sum of two or more
steps, the enthalpy change for the
overall equation is the sum of the
enthalpy changes for the individual
steps.
• Basically, R & P in individual steps can be
added like algebraic quantities in determining
overall equation and enthalpy change.

15
simple example :
Given: A + D  E + C H = X kJ
2A + B  2C H = Y kJ

1. Correct side?
Question: 2D  B + 2E H = ?
2. Correct # moles?
2A + 2D  2E + 2C H =
2X kJ
2C  2A + B H =
_______________________________________
-Y kJ
2D  B + 2E H = 2X –
Y kJ

16
 Hess’s Law
• For example, suppose you are given the
following GIVEN data:
o
S(s )  O 2 (g )  SO 2 (g ); H  -297 kJ x2
o
2SO 3 (g )  2SO 2 (g )  O 2 (g ); H  198 kJ flip
• use these data to obtain the enthalpy change for
the following reaction?
o
2S(s )  3O 2 (g )  2SO 3 (g ); H  ?

17
 o
S(s )  O 2 (g )  SO 2 (g ); H  -297 kJ x2
o
2SO 3 (g )  2SO 2 (g )  O 2 (g ); H  198 kJ flip
• If we multiply the first equation by 2 and
reverse the second equation, they will
sum together to become the third.
o
2S(s )  2O 2 (g )  2SO 2 (g ); H  (-297 kJ)  (2)
2SO 2 (g )  O 2 (g )  2SO 3 (g ); H o  (198 kJ)  (-1)
o
2S(s )  3O 2 (g )  2SO 3 (g ); H  -792 kJ

HW 45 code: ten 18
 29.6 Standard Enthalpies of
Formation
(molecular scale)
• The standard enthalpy of formation of a substance,
denoted Hfo, is the enthalpy change for the
formation of one mole of a substance in its
standard state from its component elements in
their standard state (298K & 1 atm).
Ag (s) + ½ Cl2 (g)  AgCl (s) Hfo AgCl
– Note that the standard enthalpy of formation for a
pure element in its standard state and H+ is zero.
This means elements in their standard state has
Hfo = 0: metals - solids, diatomic gases, H+ ion.

19
 Standard Enthalpies of Formation
• Another way to determine heat of
reaction is the The law of summation
of heats of formation which states that
the enthalpy of a reaction is equal to the
total formation energy of the products
minus that of the reactants.
H   nH (products )   nH (reactants )
o o
f
o
f
  is the mathematical symbol meaning “the sum
of”, and n is the coefficients of the substances in
the chemical equation.

20
Ex. Generic Law of Summation

aA + bB  cC + dD

H   nH (products )   nH (reactants )

o o
f
o
f

21
 A Problem to Consider
4NH 3 (g )  5O 2 (g )  4NO(g )  6H 2O(g )
H of :  45.9kJ / mol 0 90.3  241.8
– What is the standard reaction enthalpy , Horxn, for
this reaction?

H   nH ( products )   nH (reactants )

o o
f
o
f

22
 4NH 3 (g )  5O 2 (g )  4NO(g )  6H 2O(g )
H of :  45.9kJ / mol 0 90.3  241.8
• Using the summation law:
H   nH f (products)   mH f (reactants)
o o o

H o  [4molNO (90.3kJ / molNO )  6molH 2O(241.8kJ / molH 2O)]

 [4molNH 3(45.9kJ / molNH 3)  5molO 2(0kJ / molO 2)] 
 [361.2kJ  (1450.8kJ )]  [(183.6kJ )  0kJ ] 
 1089.6kJ  183.6kJ  906kJ
o HW 46
H  906 kJ code: formation
– Be careful of arithmetic signs as they are a
likely source of mistakes.
23
 35.1.2 The Second Law of
Thermodynamics
• The second law of thermodynamics
addresses questions about spontaneity
in terms of a quantity called entropy.
– Entropy, S , is a thermodynamic quantity
that is a measure of the randomness or
disorder of a system.
– The SI unit of entropy is joules per Kelvin
(J/K) and, like enthalpy, is a state function.

24
 absorb E, nonspon (endo)
release E, spon (exo)
P
R

E P E R

Most soluble salts dissolve in water spontaneously; however,

most soluble salts dissolve by an endothermic process.

NH4NO3 (s)  NH4+ (aq) + NO3- (aq) H = 28.1 kJ

There is an increase in molecular disorder or randomness of the system.

Solids: high order/low disorder, high energy

Liquids: middle order/low disorder, medium energy
Gases: low order/high disorder, low energy
25
entropy (S) - is a thermodynamic quantity that is a measure of how dispersed the
energy of a system is among the different possible ways that system can contain
energy, typically in J/K units.
One example of entropy is the amount of molecular disorder or randomness in
the system.
S increases as disorder increases and energy decreases
gases have high disorder, low energy
solids have low disorder, high energy
We typically follow the change in entropy in the system so we treat it as a state
property and measure S = Sfinal - Sinitial
+ S = increase in entropy, i.e. disorder increased; -U
-S = decrease in entropy, ie. disorder decreased ; +U
This gets us to the second law of thermo

26
 Entropy and the Second Law of
Thermodynamics

• The second law of thermodynamics

states that the total entropy of a system
and its surroundings increases for a
spontaneous process.

27
The tendency of a system to increase its entropy (+S) is the second important
factor in determining the spontaneity of a chemical or physical change in addition
to H.
recap:
spontaneous process: (system goes to lower energy state)
favored by -H (exo)
favored by +S (ie. increase disorder)
nonspontaneous process: (system goes to higher energy state)
favored by +H (endo)
favored by -S (ie. decrease in disorder)
Do both need to be true for spon rxn? No, remember soluble salt dissolving
example. The larger term will dictate overall process.

28
35.4 Third Law of Thermodynamics
• The third law of thermodynamics states that the
entropy of all perfect crystalline substances
approaches zero as the temperature approaches
absolute zero (Kelvin).
– As temperature is raised the substance
becomes more disordered as it absorbs
heat and becomes a liquid then a gas,
where entropy > 0; S increases as temp
increase.
– The entropy of a substance is determined
by measuring how much heat is required to
change its temperature per Kelvin degree
(J/K). 29
 35.5 Standard Reaction Entropy

• The standard entropy of a substance

or ion, also called its absolute entropy,
So, is the entropy value for the standard
state of the species. Similar to heats of
formation, Hfo , except on absolute not
relative scale.
– Standard state implies 25 oC (298K), 1 atm
pressure, and 1 M for dissolved
substances.(Thermo standard state)

30
Standard Entropies and the Third Law
of Thermodynamics
– This means that elements have nonzero values
for entropy (absolute scale), unlike standard
enthalpies of formation, Hfo , which by
convention, are zero (relative scale).
– The symbol So, rather than So, is used for
standard entropies to emphasize that they
originate from the third law and absolute not
relative values.

31
 Entropy Change for a Reaction
• You can calculate the entropy change
for a reaction using a summation law,
similar to the way you obtained Hfo.
S   nS (products )   mS (reactants )
o o o

– Even without knowing the values for the entropies

of substances, you can sometimes predict the sign
of So for a reaction.

32
Entropy Change for a Reaction
The entropy usually increases in the
following situations:
1. A reaction in which a molecule is broken into
two or more smaller molecules.
AB  A + B +S
2. A reaction in which there is an increase in the
moles of gases.
A(g)  B(g) + C(g) +S
3. A process in which a solid changes to liquid
or gas, or a liquid changes to gas.
A(s)  B(l) or B(g) +S
B(l)  C(g) +S
33
Predict S and spon/nonspon based only on entropy for the following rxns:
C2H4 (g) + Br2 (g)  BrCH2CH2Br (l)

gas to liquid; decrease in disorder; -S;

nonspon based on S only

2 C2H6 (g) + 7 O2 (g)  4 CO2 (g) + 6 H2O (g)

9 mols gas to 10 mols of gas; increase in
disorder; +S; spon based on S only
HW 47
C6H12O6 (s)  2 C2H5OH (l) + 2 CO2 (g) code: ben
solid to liquid/gas (decompose); increase in
disorder; +S; spon based on S only

34
 A Problem To Consider
• Calculate the change in entropy, So, at 25oC
for the reaction in which urea is formed from
NH3 and CO2.

2NH 3 (g )  CO 2 (g )  NH 2CONH 2 (aq )  H 2O(l )

– The calculation is similar to that used to obtain

Ho from standard enthalpies of formation.

Gas to liquid; decrease in disorder; predict -S

35
 A Problem To Consider

2 NH 3 ( g )  CO2 ( g )  NH 2CONH 2 (aq )  H 2O(l )

So: 193 J/mol.K 214 174 70

S   nS (products )   mS (reactants )
o o o

S o  [(1molNH 2CONH 2 )(174 J / molK )  (1molH 2O)(70 J / molK )]

 [(2molNH 3 )(193 J / molK )  (1molCO2 )(214 J / molK )]  356 J/K

decrease in disorder as predicted

36
 35.6 Gibbs Free Energy

• The question arises as to how do we decide if enthalpy or

entropy dictates the spontaneity of a reaction. What is the
relationship between H and S?
• The American physicist J. Willard Gibbs introduced the
concept of free energy (sometimes called the Gibbs free
energy), G, which is a thermodynamic quantity defined by
the equation
 G=H-TS T – Kelvin scale

– This quantity gives a direct criterion for

spontaneity of reaction.

37
 Free Energy and Spontaneity
• Changes in H an S during a reaction result in a change in free
energy, G , given by the equation

G  H  T S
At a given temperature and pressure
G = 0, the reaction gives an equilibrium mixture with
significant amounts of both reactants and products (Temp
transfer point where reaction switches spon/nonspon)
G > 0 , the reaction is nonspontaneous as written, and
reactants do not give significant amounts of product at
equilibrium.
G < 0 , the reaction is spontaneous as written, and the
reactants transform almost entirely to products when
equilibrium is reached.
38
  G  H  T S
• Lets look at relationship among the signs of H, S and G and
spontaneity. Note that temperature will dictate which will rule. Also realize
T is in K meaning no negative temp.

H S G Description
– (exo) +disorder – Spontaneous at all T
spon spon spon

+ (endo) –disorder + Nonspontaneous at all T

non non non
Spontaneous at low T (room); H > TS; -G
– (exo) –disorder + or – Nonspontaneous at high T (1000K); H < TS
Spon non +G

Nonspontaneous at low T; H > TS; +G

+ (endo) +disorder + or – Spontaneous at high T; H < TS; -G
Non spon
enthalpy rules at low temp but entropy at very high T 39
35.7 Gibbs Energy and Equilibrium
• The standard free energy change, Go,
is the free energy change that occurs
when reactants and products are in their
standard states.
– The next example illustrates the calculation
of the standard free energy change, Go,
from Ho and So.
o o o
 G   H  T S
40
 A Problem To Consider

• What is the standard free energy change, Go,

for the following reaction at 25oC?

N 2 (g )  3H 2 (g )  2NH 3 (g ) predict
Hfo: 0 0 -45.9 kJ/mol H, spon
So: 191.5 130.6 193 J/mol K S, nonspon
G, spon

41
 N 2 ( g )  3H 2 ( g )  2 NH 3 ( g )
Hfo: 0 0 -45.9 kJ/mol
So: 191.5 130.6 193 J/mol K
H o   nH of (products)   mH of (reactants)
 [2molNH 3  (45.9kJ / mol )]  [0]  91.8 kJ
S   nS (products )   mS (reactants )
o o o

 [(2molNH 3 )(193J / molK )]  [(1molN 2 )(191.5 J / molK )

 (3molH 2 )(130.6 J / molK )]  -197 J/K  -0.197 kJ/K
– Now substitute into our equation for Go. Note that
So is converted to kJ/K and Kelvin for temp.
o o o
 G   H  T S
 91.8 kJ  (298 K)( 0.197 kJ/K)
 33.1 kJ spon rxn as written 42
Standard Free Energies of Formation
• The standard free energy of formation,
Gfo, of a substance is the free energy
change that occurs when 1 mol of a
substance is formed from its elements in their
stablest states at 1 atm pressure and 25oC.
– By tabulating Gfo for substances, you can
calculate the Go for a reaction by using a
summation law.

G  
o o
nG f (products)   o
mG f (reactants)

43
 A Problem To Consider
• Calculate Go for the following reaction at
25oC using std. free energies of formation.

C2 H 5OH (l )  3O2 ( g )  2CO2 ( g )  3H 2O ( g )

Gfo: -174.8 0 -394.4 -228.6 kJ/mol

G  
o o
nG f (products)   o
mG f (reactants)
G o  [(2molCO2 )(394.4kJ / mol )  (3molH 2O)(228.6kJ / mol )]
 [(1molC2 H 5OH )(174.8kJ / mol )  0] 

G o  1299.8 kJ spon rxn

44
 Relating Go to the Equilibrium
Constant
• The free energy change (G) when
reactants are in non-standard states
(meaning other than 298K, 1 atm
pressure or 1 M) is related to the
standard free energy change, Go, by
the following equation.
o
G  G  RT ln Q
– Here Q is the thermodynamic form of the
reaction quotient ([products]/[reactants] not
necessarily at equil); T in kelvin; R=8.31 J/molK.
45
Relating Go to the Equilibrium
Constant
– G represents an instantaneous change in
free energy at some point in the reaction
approaching equilibrium G=0.

G  G  RT ln Q
o

– At equilibrium, G=0 and the reaction

quotient Q becomes the equilibrium
constant K.
o
0  G  RT ln K
46
 Relating Go to the Equilibrium
Constant
• This result easily rearranges to give the
basic equation relating the standard
free-energy change to the equilibrium
constant.
o
G   RT ln K
– When K > 1 (meaning equil lies to the
right), the ln K is positive and Go is
negative (spon).
– When K < 1 (meaning equil lies to the left),
the ln K is negative and Go is positive
(nonspon). 47
 A Problem To Consider
• Find the value for the equilibrium constant, K,
at 25oC (298 K) for the following reaction. The
standard free-energy change, Go, at 25oC
equals –13.6 kJ/mol.
2NH 3 (g )  CO 2 (g ) NH 2CONH 2 (aq)  H 2O(l )

– Rearrange the equation Go= -RTlnK to give

o
G
ln K 
 RT

48
 A Problem To Consider
o
G
ln K 
 RT
– Substituting numerical values into the equation,

 13.6  10 J / mol
3
ln K   5.49
 8.31 J/(mol  K)  298 K

K e 5.49
 2.42 10  240
2

49
 Calculation of Go at Various
Temperatures
• We typically assume that Ho and So are
essentially constant with respect to
temperature.

– You get the value of GTo at any temperature T by

substituting values of Ho and So at 25 oC into the
following equation.

o o o
G T   H  T S
50
 A Problem To Consider

• Find the Go for the following reaction at 25oC

and 1000oC. Relate this to reaction
spontaneity.
CaCO 3 (s )  CaO(s )  CO 2 (g )
Hfo: -1206.9 -635.1 -393.5 kJ/mol
So : 92.9 38.2 213.7 J/mol K

51
 CaCO 3 (s )  CaO(s )  CO 2 (g )
Hfo: -1206.9 -635.1 -393.5 kJ/mol
So : 92.9 38.2 213.7 J/mol K
H o   nH of (products)   mH of (reactants)
 [( 635.1  393.5)  ( 1206.9)]kJ  178.3 kJ
S   nS (products )   mS (reactants )
o o o

 [(38.2  213.7)  (92.9)]  159.0 J / K  0.1590 kJ/K

o o o
G T   H  T S
– Now you substitute Ho, So (=0.1590 kJ/K), and
T (=298K) into the equation for Gfo.
G25o o C  178.3kJ  (298 K )(0.1590 kJ / K )
So the reaction is
nonspontaneous
G25
o
o
C
 130.9 kJ at 25oC. 52
 A Problem To Consider
• Find the Go for the following reaction at
1000oC.
– Now we’ll use 1000oC (1273 K) along with our
previous values for Ho and So because assume
does not change much.

G o
1000o C
 178.3kJ  (1273 K )(0.1590 kJ / K )
G o
1000o C
 24.1 kJ So the reaction is
spontaneous at
1000oC.
You see that this reaction change from nonspon to spon
somewhere between 25oC to 1000oC. How can we determine at
what temp this switch occurred? G=0 is equil, switch point
53
 – To determine the minimal temperature for
spontaneity, we can set Gº=0 and solve for T.
G o  0  H o  TS o
H o  TS o CaCO 3 (s )  CaO(s )  CO 2 (g )

H o nonspon < 848oC; CaCO3 stable

T spon > 848oC; CaCO3 decomposes easily
S o
178.3 kJ o
T  1121 K (848 C) HW 48
0.1590 kJ / K code: six
– Thus, CaCO3 should be thermally stable until its
heated to approximately 848 oC.
– This is way you could calculate the normal boiling
point of a liquid. At G=0, the liquid phase and l  g
gas phase will be at equilibrium; temperature at
which switch from liquid to gaseous phase. 54