6/14/2020

THERMOCHEMISTRY

1
Thermochemistry:
Energy Flow and Chemical Change

• All changes in matter - accompany by changes in the energy

content of the matter.

6/14/2020
• e.g. Snow melts - energy is absorbed
Water vapor condenses to rain - energy is release
• Investigation of heat associated with changes in matter.
• thermodynamic & thermochemistry should be examined

• Thermodynamics: the study of energy transfer & its

transformation.

• Thermochemistry: branch of thermodynamics; deals with

energy absorbed/released by chemical reactions.
2
• the study of how energy in the form of heat is involved in
chemical change
 State functions
• A state function describes the equilibrium state of a system.
describe quantitatively an equilibrium state of a thermodynamic
system, irrespective of how the system arrived in that state

6/14/2020
Path independent
• E.g: Changes in state function (such as E, P, V) depend only on
the initial and final states of the system.
• Symbols for state functions (such as E, P, V) are capitalized.

Thermodinamics variables;
• Internal energy, ∆E
• Enthalpy, ∆H
• Entropy, ∆S
3
• Gibb free energy, ∆G
State Functions and
the Path Independence of the Energy Change

• System’s internal energy, E state of function property is

6/14/2020
determined by the current state of the system;
• not dependent on the path the system took to
reach the state

• Heat, q and work, w are not state functions

their values depend on the path the system takes in
undergoing the energy change
• For a given change, E (sum of q and w) is constant,
even though the specific values of q and w can vary
4
Energy and Their Interconversion
The system and Its Surroundings;

6/14/2020
• System: part of universe whose change to be observed
• Surroundings: everything relevant to the change of the
system

• System must be defined - to make a meaningful

observation
measurement of a change in energy

5
Energy
The capacity of something to do work
• chemical, mechanical, thermal, electrical, radiant, sound,
nuclear

6/14/2020
• Reactants → Products
• Energy + Reactants →Products
• Reactants →Products + Energy

• Work; the simplest definition being the force involved in moving

an object some distance.
• SI unit = Joule (J)
• Others; Calories (cal), Kilowatt-hour (kW.hr)

• Law of conversion of energy;

• Energy cannot be created nor destroyed 6
• it can only change from one type to another!
Energy is the capacity to do work;
• Thermal energy is the energy associated with the
random motion of atoms and molecules

6/14/2020
• Chemical energy is the energy stored within the bonds of
chemical substances
• Nuclear energy is the energy stored within the collection
of neutrons and protons in the atom
• Electrical energy is the energy associated with the flow of
electrons
• Potential energy is the energy available by virtue of an
object’s position
7
• In chemical reactions, energy :
is required to break bonds (energy absorbed)
is released when bonds are formed

• Bond Energy = The amount of energy required to break a

6/14/2020
chemical bond is the same as the energy released when
the bond is formed.

• During a chemical reaction, energy :

• absorbed = the bond energies for all bonds broken in
the reactants
• released = the bond energies for all bonds formed in
the products
8
 Kinetic and Potential Energy
• All energy (potential or kinetic) - convertible from one to the other
• An object has:
1. potential energy (PE) by virtue of its position
2. kinetic energy (KE) by virtue of its motion

6/14/2020
• Kinetic energy (KE); energy an object has when it is moving;
1
KE = 𝑚𝑣 2
2

• Potential energy (PE); Stored energy; energy an object has that

can be change to kinetic energy
• Depends on position;
 Increases when objects that attract move apart; decreases when
move towards
 Increases when objects that repel move towards each other; 9
decreases when move apart
Change in internal energy
a transfer of energy from system to surroundings & vice versa
• Internal energy, E = Sum of potential and kinetic energy for all
the particles in the system.

6/14/2020
• E = Change or difference in internal energy
• difference between the system’s internal energy after the
change (Efinal) and before the change (Einitial)

E = Efinal - Einitial = Eproducts – Ereactants

• A reacting chemical system can change its internal energy in

either of 2 ways by:
1. losing some energy to surroundings: Efinal  Einitial 10
2. gaining some energy from surroundings: Efinal > Einitial
Homeworks
• Lifting of book

6/14/2020
• Toss a ball into the air
• The motion of a person on a swing

11
Heat
 Heat is the transfer of thermal energy between two bodies
that are at different temperatures
 is the form of energy that flows due to a temperature

6/14/2020
difference.

• flows from higher temperature to lower temperature (hot

objects to cold objects)
 is transferred due to “collisions” between atoms/
molecules of different kinetic energy
• is absorbed/released; measured by changes in temperature

• A friction of heat is mechanical energy that is irretrievably

12
removed from a system
Specific Heat Capacity (s)

The amount of heat energy (in J or Cal) required to

increase the temperature of 1 gram of a substance by 1°C

6/14/2020
(or 1K)
• Units; J/g°C (SI), cal/g°C (metric & more useful in the lab)

• Specific Heat Capacity of substances of different property is

unique. E.g;
• Metals have low specific heat capacity
• Non-metals have higher specific heat capacity
• Water has an unusually large specific heat capacity

s = Q/(m∆T) 13
 6/14/2020
14
 Table of Specific Heat for various substances @ 20oC
c in cal/gm K or Molar C
Substance c in J/gm K
Btu/lb F J/mol K
Aluminum 0.900 0.215 24.3
Bismuth 0.123 0.0294 25.7

6/14/2020
Copper 0.386 0.0923 24.5
Brass 0.380 0.092 ...
Gold 0.126 0.0301 25.6
Lead 0.128 0.0305 26.4
Silver 0.233 0.0558 24.9
Tungsten 0.134 0.0321 24.8
Zinc 0.387 0.0925 25.2
Mercury 0.140 0.033 28.3
Alcohol(ethyl) 2.4 0.58 111
Water 4.186 1.00 75.2
Ice (-10 C) 2.05 0.49 36.9 15
Granite .790 0.19 ...
Glass .84 0.20 ...
Heat & Temperature

• Heat is the transfer of thermal energy between two

bodies that are at different temperatures

6/14/2020
• Temperature is a measure of the thermal energy
• Temperature (T) is the degree of intensity of hotness
or coldness
how hot or cold something is (a physical property).
• related to the average (kinetic) energy of the
substance (not the total energy).

16
Heat Transfers
• Exothermic process is any process that gives off heat –
transfers thermal energy from the system to the

6/14/2020
surroundings.
2H2 (g) + O2 (g) 2H2O (l) + energy
H2O (g) H2O (l) + energy

• Endothermic process is any process in which heat has to be

supplied to the system from the surroundings.
• E.g; melting ice to form liquid water is an endothermic
process.
energy + H2O (s) H2O (l) 17

6.2
Temperature of ice water and boiling water.

6/14/2020
18
Heat & Temperature Measurement
• Temperature is measured in units of
• Degrees Fahrenheit (°F)
• Water’s freezing point = 32F, boiling point = 212F
• Degrees Celsius (°C)

6/14/2020
• Temperature unit larger than the Fahrenheit
• Water’s freezing point = 0°C, boiling point = 100°C
• Kelvin (K)
• Temperature unit same size as Celsius
• Water’s freezing point = 273 K, boiling point = 373 K

• The heat energy absorbed by an object is proportional to;

• mass of object (m) and change in temperature the object
undergoes (∆T)
Heat (Q): Q = s . m . ∆T
• s = specific heat capacity (a physical property unique to the 19
substance)
Heat and Work:
Two Forms of Energy Transfer
• Energy transfer outward from the system or inward from the
surroundings can appear in two forms; heat & work
• Total change in a system’s internal energy: E = q + w

6/14/2020
• 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 by a force

• q & w can be either +ve/-ve:

20
• energy into the system: +ve
• energy out from the system: -ve
 Energy Flow to and from a System
• Energy diagrams for the transfer of internal energy (E)
between a system and its surroundings

6/14/2020
E = q + w
21
• Total change in a system’s internal energy:
Energy transfer as heat only

system that does no work but transfers energy as heat (q)

• Work, w = 0.  E = q

6/14/2020
22
• Heat out from a system – hot water in a beaker
• System – hot water

6/14/2020
• q = -ve as heat was lost by the system.
E = -ve

• Heat into a system - Ice water in a beaker

• System: ice water
• q = +ve as heat was gained by the system.
• E = +ve 23
Energy transfer as work only
1. Work done on a system
• Heat , q = 0 E = w
• If the external pressure on the piston is increased, the

6/14/2020
work is done on the system by the surroundings.
System gains energy, w = +ve, E = +ve

24
2. 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

6/14/2020
Zn (s) + 2H+ (aq) +  H2(g) + Zn2+ (aq) + 2Cl-(aq)

• As the H2 gas forms, the system used some of the

internal energy to do work on the surroundings and
push the piston outward.
  Energy is lost by the system as work, w = -ve,
 E = -ve
25
• q = +ve : system gains heat (energy),
• q = -ve: system loses energy

6/14/2020
• w = +ve: work done on system
• w = -ve: work done by system

26
The Law of Energy Conservation /
The First Law of Thermodynamics
• Law of Energy Conservation; Energy ..
can be converted from one to another

6/14/2020
cannot simply appear or disappear
cannot be created or destroyed

• First Law of Thermodynamics: the total energy for an

isolated system is constant
• Energy of system + energy of surroundings remains
constant: energy is conserved
• A mathematical expression;
Euniverse = Esystem + Esurroundings = 0 27
Units of Energy
• SI unit = Joule (J)
• 1 cal (non SI unit) = 4.184 J

6/14/2020
• Heat, work, potential energy, kinetic energy are
expressed in Joules

• In the case of work:

• Work, w = Force (F) x distance (d)
where F = mass (m) x acceleration (a) in units of kgm
s2
2
• w = kg m kg m
2
xm 2
J
s s 28
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 car’s cooling system.

6/14/2020
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
Plan: 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 29
Calculating E in J:
q = -325 J, w = -451 J,

6/14/2020
E = q + w
= -325 J + (-451J) = -776 J

30
Enthalphy:
Exothermic and Endothermic Processes
• Enthalphy is a state function defined by the equation;
H = E + PV
Enthalphy change of reaction, H = E + PV

6/14/2020
• H, is also called the heat of reaction, Hrxn;
H = Hfinal - Hinitial = Hproducts – Hreactants

• 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
31
• results in an increase in the enthalphy
• Endothermic: Hfinal  Hinitial, H  0/+ve
Enthalpy (H) is used to quantify the heat flow into or out of a system
in a process that occurs at constant pressure.
∆H = H (products) – H (reactants)
∆H = heat given off or absorbed during a reaction at constant
pressure

6/14/2020
32
Hproducts < Hreactants Hproducts > Hreactants
∆H < 0 ∆H > 0
Example

In each of the following cases, determine the sign of H, state

whether the reaction is exothermic or endothermic

6/14/2020
(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 = Hproducts - Hreactants 0

and the reaction is exothermic
(b) Heat is a reactant (on the left), so H = Hproducts - Hreactants  0
and the reaction is endothermic

33
Enthalphy:
Heats of Reaction and Chemical Change
H = E + PV
Change in Enthalpy , H = E + PV

6/14/2020
• Heat & work must be measured to determine total change
in a system’s internal energy: E

• Two most important type of chemical work

(i) electric work - work done by moving charged particles
(ii) PV work - work done by expanding gas
quantity PV work = multiple the external pressure (P) by
the change in volume of the gas (V, or Vfinal - Vinitial)
34
w = - PV
• e.g. In an open flask, a gas done work by pushing back
the atmosphere.

6/14/2020
• Work done on the surroundings is -ve because the
system loses energy
w = -PV

• For reactions that occur at constant pressure, a

thermodynamics variable called enthalphy (H) includes
the need to consider PV work.

35
• w = -PV
• E = q + w

• Combining Equations

6/14/2020
E = q + w
= q + (- PV) = q - PV

• At constant pressure, q = qp
E = qp - PV
qp = E + PV
36
where E + PV = H
Comparing E and H
• For many reactions, H is equal / very close to E.
• Three cases;
1. Reactions that do not involve gases

6/14/2020
• e.g. 2KOH(aq) + H2SO4(aq)  K2SO4(aq) + 2H2O(l)
• Liquids & solids undergo very small volume changes;
V 0, PV  0, H  E

2. 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); 37

V = 0, PV = 0, H  E
3. Reactions in which the amount (mol) of gas does
change.

6/14/2020
• PV  0, qp is usually much larger than PV

• From equation;
•
q p =  E + P V =  H
E = qp - PV = H,
E  qp  H,
  E  H 38
Important Types of Enthalpy Change
(i) Heat of combustion (Hcomb):
when 1 mole of substance combines with O2 in a
combustion reaction

6/14/2020
e.g. C4H10(l) + 13/2 O2(g)  4CO2(g) + 5H2O, H = Hcomb
(ii) Heat of formation (Hf):
when 1 mole of compound is produced from its element
e.g. K(s) + 1/2 Br2 (l)  KBr(s), H = Hf
(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):
39
when 1 mole of substance vaporize
• The only reaction when H and E differ by significant
amount is when;
Gases are formed or consumed in a reaction
• Assume gas behave as ideal gases

6/14/2020
• When reaction occurs, V change is cause by a
change in the number of moles of gas, n
∆𝒏𝒈𝒂𝒔 = 𝒏𝒈𝒂𝒔 (𝒑𝒓𝒐𝒅𝒖𝒄𝒕) − 𝒏𝒈𝒂𝒔 (𝒓𝒆𝒂𝒄𝒕𝒂𝒏𝒕)
𝑹𝑻
𝑷𝑽 = 𝒏𝑹𝑻, 𝑷∆𝑽 = 𝑷 × ∆𝒏𝒈𝒂𝒔 = ∆𝒏𝒈𝒂𝒔 𝑹𝑻
𝑷

• Substituting equation for H gives;

∆𝑯 = ∆𝑬 + ∆𝒏𝒈𝒂𝒔 𝑹𝑻
∆𝑬 = ∆𝑯 − ∆𝒏𝒈𝒂𝒔 𝑹𝑻 40
Calorimetry: Laboratory Measurement of Heats
of Reaction

• Enthalphy of a system in a given state - cannot be measured

• Change in enthalphy - can be measured; Specific Heat Capacity

6/14/2020
• Quantity of heat (q) absorbed by an object is proportional to its
temperature change;
q  T or q = constant x T or q/T = constant
• Heat capacity, C = q/T = quantity of heat required to change
the temperature of substance by 1K. (Unit: J/K)
• Specific heat capacity, c = q/(mxT) = quantity of heat required
to change the temperature of 1 gram of a substance by 1K (Unit:
J/g.K) 41
Heat absorbed or released, q = c x mass x T
Example

A welded layer of copper on the bottom of a skillet weighs

125 g. How much heat is needed to raise the

6/14/2020
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
42
The Practice of Calorimetry

• Calorimeter - used to measure the heat

released/absorbed by a physical or chemical process.

6/14/2020
• 2 common types:
1. constant-pressure; 2. constant-volume calorimeters

Constant-Pressure Calorimetry
1. A coffee-cup calorimeter
• Use to measure the heat (qp) of many processes that
are open to the laboratory atmosphere
• Common use - to determine the specific heat capacity
of a solid (does not react/dissolve in water)
43
• Process:
• solid (system) is weighed, heated to some known
temperature, added to a sample of water
(surroundings) of known temperature & mass in the
calorimeter

6/14/2020
• Continual stirring which distribute the released heat
• Final water temperature (final temperature of the
solid) is measured

44
• Heat lost by the system (-q) is equal in magnitude but
opposite in sign to the heat gained (+q) by the

6/14/2020
surroundings:

• Heat absorbed or released, q = c x mass x T

• -qsolid = qH2O, substituting in equation

• -(csolid x masssolid x Tsolid) = cH20 x massH20 x TH20
• All the quantities are known except csolid

45
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

6/14/2020
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.
• Calculating csolid
J
4.184 x 50.00 g x 3.39 K
c H 2O x mass H 2O x ΔTH 2O gK
c solid   
masssolid x ΔTsolid 25.64 g x (71.51 K)
46
J
 0.387
gK
Constant-Volume Calorimetry
2. Common type: bomb calorimeter
• Use to measure very precisely the heat released in
combustion reaction

6/14/2020
• Knowing mass of the sample and the heat capacity of
the calorimeter, the measured T is used to calculate
the heat released.

47
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

6/14/2020
increases 4.9370C. Is the manufacturer’s 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
48
= 8.151 J/k x 4.937 K
= 40 J = 9.56 cal (1cal = 4.184 J)
Stoichoimetry of Thermochemical Equations
• Thermochemical equations
• a balanced equation that states the heat of reaction (Hrxn)
 Hrxn value refers to the enthalphy change for the amounts of
substances in that specific reaction.

6/14/2020
• Two aspects of enthalphy change:
(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
Formation of 2 mol water (exothermic):
2H2(g) + O2(g)  2H2O(l) Hrxn = -572 kJ 49
(ii) Magnitude
• Magnitude of H is proportional to the amount of

6/14/2020
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

50
Hess’s Law of Heat Summation
• Enthalpy is a state function, which means its value for a
system depends only on the current state of the system and
not on its history.
• the change depends only on the initial and final states for a

6/14/2020
system and not on the path between the two
• The state function nature of enthalpy is expressed in Hess’s
Law

• Hess’s Law - the difference between the enthalpies of the

reactant and the product has the same value even though
the reaction takes place differently.
• Hess’s law of heat summation: if a chemical reaction can be
expressed as the sum of two or more chemical reactions, the 51
enthalpy change for the net reaction is equal to the sum of
the enthalpy changes for the individual steps
Calculating an unknown H
• Involves three steps:
(i) identify the target equation, note the number of moles of

6/14/2020
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 reverse 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). 52
Add their H values to obtain the unknown H
Example
• Application of Hess’s Law:

Oxidation of sulfur trioxide

6/14/2020
Eq. 1: S(s) + O2(g)  SO2(g) H1 = -296.8 kJ
Eq. 2: 2SO2(g) + O2(g)  2SO3(g) H2 = -198.4 kJ
Eq. 3: S(s) + 3/2 O2(g)  SO3(g) H3 = ?

• Manipulate equation 1 and/or 2 so that they add up 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 Sulfur, so
53
leave eq. 1 unchanged
Eq. 1: S(s) + O2(g)  SO2(g) H1 = -296.8 kJ
Eq. 2: 2SO2(g) + O2(g)  2SO3(g) H2 = -198.4 kJ
Eq. 3: S(s) + 3/2 O2(g)  SO3(g) H3 = ?
Eq. 2 has twice as much SO3 as Equation 3, so multiply it by 1/2,
multiply H2 by 1/2 as well

6/14/2020
Add eq. 1 to the halved eq. 2, cancel terms that appear on both
sides:
Eq. 1: S(s) + O2(g)  SO2(g) H1 = -296.8 kJ
1/2 (Eq. 2): SO2(g) + 1/2 O2(g)  SO3(g)
1/2(H2) = -99.2 kJ

Eq. 3: S(s) + O2(g) + SO2(g) + 1/2 O2(g)  SO2(g) + SO3(g)

S(s) + 3/2 O2(g)  SO3(g)
 H3 = H1 + 1/2 (H2)
54
= -296.8 kJ + (-99.2 kJ)
= -396.0 kJ
Standard Heats of Reaction (H0rxn)
• Enthalpies vary with experimental conditions
• e.g; temperature, pressure, and solution concentration

6/14/2020
• Standard conditions for enthalpy values are;
• gases, liquids, and solids in their pure form at a pressure of
1 bar at a specified temperature
• solutions with concentrations of 1 mol/L at a specified
temperature.

• Notice that standard conditions do not specify a temperature.

• Most standard enthalpy values are tabulated at 25°C (298 K),

but it is possible to report standard enthalpy change values at
other temperatures. 55
• Standard states (a set of specified conditions and
concentration) are used to compare heats of reaction
and other thermodynamic data:
• Gas: standard state - 1 atm

6/14/2020
• Substance in aqueous solution: standard state - 1 M
• Pure substance (element or compound): standard
state: usually the most standard at 1 atm and the
temperature of interest (250C)

• A right superscript zero indicates when thermodynamics

variable has been determined with all substances in their
standard states.
• e.g. Standard heat reaction, H0rxn, is the H0rxn
measured with all substances in their standard states. 56
Formation Equations and Their Standard
Enthalpy
• In a formation equation, 1 mol of compound forms from
its elements

6/14/2020
• Standard heat of formation (H0f) for a species; is the
enthalpy change for the formation of one mole of a
species from its constituent elements in their most stable
form/standard states

• e.g.
C(graphite) + 2H2O(g)  CH4(g) H0f = -74.9 kJ

57
Example
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 -

6/14/2020
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 = -127.0 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 H0f = 135 kJ
58
 Determining H0rxn
from H0f values of Reactants and Products

• By applying Hess’s Law, H0f values can be used to

determine H0rxn for any reaction:

6/14/2020
H0rxn = mH0f (products) - mH0f (reactants)

Suppose we want H0rxn for:

TiCl4(l) + 2H2O(g)  TiO2(s) + 4HCl(g)

H0rxn = {H0f [TiO2(s)] + 4H0f [HCl(g)]} - {H0f [TiCl4(l) + 2H0f [H2O(g)]}

(Products) (Reactants)
59
 Example
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)

6/14/2020
Calculate H0rxn from H0f values

Solution
H0rxn = mH0f (products) - mH0f (reactants)

= {4H0f [NO(g)] + 6H0f [H2O(g)]} - {4H0f [NH3(g)] + 5H0f [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 60
= -906 kJ
Chemical Thermodynamics
• Area of chemistry that explores energy relationship
• Limitations of First Law Thermodynamics
• only tells the amount of heat released/work done by the

6/14/2020
system & the amount of heat gained/work done on the system
• sign of enthalpy, H is not enough to predict whether the
reaction will proceed
• H is not the only factor governs
• reactants or products should also be favoured
• Reactants or products favoured;
In addition to H, change in randomness or disorder in
chemical reaction is considered
• New aspect in discussion of thermodynamics
61
spontaneous process related to disorder in chemical reaction
Entropy & the Second Law of
Thermodynamics
• Entropy, S - a thermodynamic quantity - a measure of the
randomness/disorder of a system.

6/14/2020
• 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
• Solids: have much more regular structure than liquids.
 Liquids > disordered than solids
• A gaseous state; particles in are in random motion.
 Gases > disordered than liquids
 Any process that increases the amount of particles, 62
 disorder
• Consider the melting 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

6/14/2020
a relatively low S
• In liquid water, molecules moves about freely, disordered
structure; liquid water has greater entropy than ice

• 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, implies the system becomes less disordered 63
Molecular Interpretation of Entropy
• Structure & behaviour of molecules - affect the entropy
of the system

6/14/2020
• Entropy of the system increase (S > 0) when:
(i) gas molecules spread out in a larger volume
(ii) phase changes: solid  liquid, liquid  gas
• Entropy of the system decrease (S < 0) when:
(i) condensing a gas
(ii) freezing a liquid
• A reaction leads to a decrease in the number of gaseous
molecules 64
• generally leads to a decrease in entropy
• e.g. 2NO(g) + O2(g)  2NO2(g)

6/14/2020
• entropy change = -ve because 3 molecules of gas react
to form 2 molecules of gas
• formation of new N-O imposes more order, atoms
are more “tied up” in the products than in the
reactants
• leads to a decrease in the entropy

65
• In general - the greater the no. of freedom of system, the
greater its entropy
• Formation of the new bonds –
• decreases the number of degrees of freedom/ forms of
motion
atoms are less free to move in random fashion

6/14/2020
• The degrees of freedom of molecules - associate with three
types of motion for the molecule:
(i) Translational motion
(ii) Vibrational motion
(iii) Rotational motion

• In general, the entropy is expected to increase when:

(i) Liquids or solutions are formed from solids
(ii) Gases are formed from either solids or liquids 66
(iii) No. of molecules of gas increases during a chemical reaction
Calculation of Entropy Changes

• In general - entropy increasing with increasing temp.

• Entropy of the phases of a substance: Ssolid < Sliquid < Sgas

6/14/2020
• Standard molar entropies, S0 - molar entropy values of
substances in their standard states
• Entropy change in a chemical reaction, S0;

ΔSo = ΣnSo products - Σm So reactants

 = “sum of”
n = amounts (mol) of the products 67
m= amounts (mol) of the reactants
Example

• Choose the substance that has greater entropy in each pair,

and explain your choice:

6/14/2020
(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
(a) Gaseous HCl has the higher entropy because gases are more
disordered than solids
(b) The sample containing 2 mol of HCl has twice the entropy of
the sample containing 1 mol
(c) The gaseous N2 sample has the higher entropy because
gases are more disordered than solids 68
Spontaneous Process
• Spontaneous process: Chemical or physical change occurs by
itself
• requires no continuing outside agency
• or occurs without any outside intervention

6/14/2020
• E.g; A rock at the top of a hill
• rolls down by itself - occur spontaneously / naturally
• rolls up - not natural process / non spontaneous: require
work

• Temperature: have an impact on the spontaneity

• e.g. endothermic process of melting ice, T  00C
• ice melts spontaneously
• reverse process (liquid water), not spontaneous
• But at T 00C
69
• liquid water converts into ice spontaneously
• conversion of ice liquid water, not spontaneous
Second Law of Thermodynamics
• Second Law of Thermodynamics: (∆Stotal > 0)
total entropy of a system and its surroundings always
increases for a spontaneous process

6/14/2020
• The difference between the entropy & energy
 energy - cannot be created or destroyed during chemical
change
 entropy-created during a spontaneous or natural process

• Consider the changes in entropy that occur in the system

• process takes place  entropy is created, at the same time
heat flows into/out of the system
• entropy accompanies that heat flow
When heat flow into the system  entropy flows into the 70
system
• For a spontaneous process carried out at a given temp.
• The second law can be restated in a form that refers only to the
system
• The change in entropy, S, of the system at a given
temperature;
q
ΔS  entropy created 

6/14/2020
T

• Quantity of entropy created during spontaneous process

• cannot be directly measured
• quantity of entropy created = +ve, by deleting it from the
right side of equation:
• S > q/T for a spontaneous process

71
Entropy Change for a Phase Transition
• The restatement of the second law: for a spontaneous process
at a given temperature;
the change in entropy of the system is greater than the heat

6/14/2020
divided by the absolute temperature, q
T
• Certain process occur at equilibrium or very close to
equilibrium  the change in entropy:

q (equilibrium process)
ΔS 
T

• Examples of phase changes under equilibrium: 72

• vaporization of a liquid, fusion of a solid
 q
ΔS =
T

• To obtain the entropy change for a phase change

• heat absorbed = heat of fusion, Hfus

6/14/2020
H fus
 entropy change , ΔSsurr 
T

where T = absolute temp. of the phase transition, 373K

Note: S - usually express in joules per Kelvin

e.g. Consider the melting of ice, Hfus 6.0 kJ (1 mol of ice)

73
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

6/14/2020
If 1 mol of liquid carbon tetrachloride 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
When liquid CCl4 evaporates, it absorbs heat:

3 J
ΔH vap 43.0 ×10 J
ΔS = = mol = 144
T 298 K mol K
74
• How thermodynamics is applied to the question of whether a
reaction is spontaneous?
 propose: a chemical reaction for the preparation of a
substance
 assume: a reaction occurs at constant T and P

6/14/2020
• e.g. For proposed reaction:
2NH3(g) + CO2(g)  NH2CONH2(aq) + H2O(l)

• A spontaneous reaction? Does it go left to right as written?

• If H & S for the reaction are knew  second law in the
form q can be used to answer the above question.
ΔS =
T

• The second law for a spontaneous reaction at constant P:

qp Δ H
Δ S> = 75
T T
ΔH
Δ S>
T
 ΔH (spontaneous reaction, constant T and P)
- ΔS  0
T
• prediction: reaction is spontaneous left to right as written

6/14/2020
ΔH - TΔS  0 (-ve)

• prediction: reaction is non-spontaneous left to right as written

• reaction is spontaneous in the opposite direction
Δ H - TΔ S> 0 (+ve)

• reaction is at equilibrium
Δ H - TΔ S = 0 76
 Example
• Calculate S0 for the synthesis of ammonia from N2(g)
and H2(g):
N2(g) + 3H2(g)  2NH3(g)

6/14/2020
• Solution
S0 = 2S0(NH3) - [S0(N2) + 3S0(H2)]
Substituting the appropriate S0 values

 J    J   J 
ΔS  2 mol1925   1mol191.5   3 mol130.6 
 mol K    mol K   mol K 
J
 - 198.3
K 77
 Gibbs Free Energy
• J Willard Gibbs (1839 -1903) - proposed a way to use H & S to
predict whether a given reaction will be spontaneous
• a new state function  Gibbs free energy (or just free energy)

6/14/2020
• Gibbs free energy, G = H - TS, T = absolute temp.
• At constant T, the change in free energy of the system, G:
G = H - TS
• If T & P are constant, the relationship between the sign of G
and the spontaneity of a reaction:
• If G = -ve, reaction is spontaneous in the forward reaction
• If G = +ve,
• reaction in the forward reaction is non spontaneous
• work must be supplied from the surroundings to make it
78
occur
• reverse reaction will be spontaneous
Standard Free - Energy Changes
• Standard free energies of formation, Gof ,are useful in
calculating the standard free energy change for chemical
process

6/14/2020
ΔGof  Σn ΔGo (products)  Σm ΔGof (reactants)

 = “sum of”
n = amounts (mol) of products
m = amounts (mol) of reactants

• Quantity of G0 tells whether a mixture of reactants and

products (under standard conditions) would :
(i) G0 < 0; spontaneously react in the forward direction to
 produce more products
79
(ii) G0 > 0; spontaneously react in the reverse direction to
 form more reactants
Example
(a) Calculate the standard free-energy change for the following
reaction at 298 K:
N2(g) + 3H2(g)  2NH3(g)

6/14/2020
(b) What is G0 for the reverse of the above reaction?

Solution
(a) ΔG o  2 molΔG fo NH3   1molΔG fo N2   3 mol ΔGfo H2 
  kJ    kJ   kJ 
 2 mol  - 16.66   1mol  0   3 mol  0 
  mol    mol   mol 
 - 33.32 kJ
(b) 2NH3(g)  N2(g) + 3H2(g), G0 = +33.32 kJ
80
Free Energy and Temperature
• Consider equation :
G = H (enthalpy term) - TS (entropy term)

• Generally H & S change very little with T.

6/14/2020
the value of T directly affects the magnitude of -TS

• As T increases, the magnitude of the term -TS increases.

become relatively more important in determining the sign &
magnitude of G

• E.g; melting of ice  liquid water (P = 1 atm)

H2O(s)  H2O(l), H > 0, S > 0
• endothermic process, H = +ve
• entropy increases during process, 81

S = +ve, -TS = -ve

• At T < 00C, magnitude of 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

• When T > 00C, magnitude of -TS > magnitude of H;

6/14/2020
-ve entropy term dominates, leading to a –ve value of G
• Melting of ice is spontaneous at T > 00C

• At normal melting point of water, T = 00C;

the two phases are in equilibrium
• At T = 0, H & -TS are equal in magnitude. 
• G = 0

• Under standard conditions (at 250C) 82

G0 = H0 - TS0
Example
• The Haber process for the production of ammonia
involves the following equilibrium:
N2(g) + 3H2(g)  2NH3(g)

6/14/2020
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
83
• Solution
(a) G0 become less negative (or more positive) with
increasing temperature. Thus the driving force for the
production of NH3 becomes smaller with increasing

6/14/2020
temperature

(b) G0 = H0 - T S0

T = 500 + 273 = 773 K
 J  1kJ 
ΔG  92.38 kJ - 773 K  - 198.3  3 
o

 K  10 kJ 
 - 92.38 kJ  153 kJ
 61kJ 84
Free Energy and the Equilibrium Constant

• Another two ways to use free energy as a powerful tool

in analysis of chemical reaction;

6/14/2020
• How to use G0 value to;
(i) calculate the value of G under non-standard
conditions
(ii) directly relate the G0 for a reaction to the value of the
equilibrium constant for the reaction

85
• Most chemical reactions occur under non-standard conditions
• Free-energy change under any other conditions:
G = G0 + RT ln Q

6/14/2020
R = ideal gas-constant, 8.314 J/mol-K
T = absolute temperature
Q = reaction quotient that corresponds to the particular reaction
mixture of interest
• Note: Suppose the general equilibrium equation:
aA + bB  cC + dD
a, b, p & q = coefficients in balanced chemical equation

C D
c

equilibriu m constant , K  a b
d

A B 86
• Q is calculated by substituting reactant and product
concentrations in the equilibrium-constant expression

6/14/2020
• Under standard conditions: [reactants] & [products] = 1
• Q = 1, ln Q = 0,  G = G0

• At equilibrium: G = 0, Q = K
G = G0 + RT ln Q
0 = G0 + RT ln K
G0 = -RT ln K
  ΔG o 
K  exp   87
 RT 