Chapter Four

Thermochemistry
─the First Law
1. General Conceptions
2. The First Law of Thermodynamics
3. Enthalpy and the Enthalpy of Chemical
Change
4. Thermochemical Equations
1. General Conception in Thermodynamics

Thermodynamics and Thermochemistry

 Thermodynamics is the science

of the relationship between heat and
other forms of energy.

Thermochemistry is the study of

the quantity of heat absorbed or
evolved by chemical reactions.
 Characteristics of Thermodynamics

 Thermodynamics can be considered as a

‘system level’ science. It deals with descriptions
of the whole system and not with interactions at
individual particles level.

– It deals with quantities (like T,P) averaged over a large collection

of entities (like molecules, atoms).

 Thermodynamics puts before us some

fundamental laws which are universal in nature
and hence applicable to fields across
disciplines. (the first, second and third laws)
 System and Surroundings
System is the region in which we are interested.
Surroundings is the rest of the universe.
 the Universe = System + Surroundings
Note:
 Some of the terms may look familiar (as they are used
in everyday language as well), but their meanings are
more ‘technical’ and ‘precise’, when used in TD and
hence we should not use them ‘casually’.
 More practically, we can consider the ‘Surroundings’ as
the immediate neighbourhood of the system (the part of
the universe at large, with which the system ‘effectively’
interacts).
 Open, Closed and Isolated Systems

Open system closed system isolated system

Type of system Interactions

Open Exchange matter and energy
Closed Exchange energy but not matter
Isolated Exchange neither energy nor matter
Note:
 Matter includes atoms, ions, electrons, etc.
 Energy may be transferred to the system as
heat, electromagnetic radiation etc.
 In TD the two modes of transfer of energy to
the system considered are Heat and Work. Heat
and work are modes of transfer of energy and
not ‘energy’ itself.
 Processes in Thermodynamics

 Isothermal process: the process takes place at constant temperature

(e.g. freezing of water to ice at –10C)
 Isobaric process: constant pressure
(e.g. heating of water in open air→ under atmospheric pressure)
 Isochoric process: constant volume
(e.g. heating of gas in a sealed metal container)
 Reversible process: the system is close to equilibrium at all times (and
infinitesimal alteration of the conditions can restore the universe
(system + surroundings) to the original state.
 Cyclic process: the final and initial state are the same. However, Q and
W need not be zero.
 Adiabatic process: dQ is zero during the process (no heat is
added/removed to/from the system)
 Temperature and Pressure

Temperature is a measure of the ‘intensity of

heat’. Heat flows from a body at higher
temperature to one at lower temperature.

In TD, temperature is a measure of the average

kinetic energy (or velocity) of the constituent
entities (say molecules).

 In TD, with the increased temperature, more and

more molecules will be promoted to higher
energy levels.
 Temperature and Pressure

 Pressure is force per unit area (usually exerted by a

fluid on a wall).
 In TD, P = momentum transferred / area / time. In the
case of gas molecules, it is the average momentum
transferred per unit area per unit time on to the flat wall.
 T and P are both state functions. Pressure is related to
momentum, while temperature is related to kinetic
energy.
Wall of a container
 Energy
 Energy: anything that has the capacity to do work.
1. Kinetic energy (Ek) is the energy associated with an
object by virtue of its motion.
2. Potential energy (Ep) is the energy an object has by
virtue of its position in a field of force.
3. Internal energy (U) is the sum of the kinetic and
potential energies of the particles making up a
substance.
• The total energy of a system is the sum of its kinetic energy,
potential energy, and internal energy.
Etot  Ek  Ep  U
Chemical energy, Electric energy, Radiant energy……
 Energy Exchange

Energy is tansfered between the system and

surroundings through either heat exchange or
work being done.
 State Function

 A property which depends only on the current

state of the system (as defined by T, P, V,  etc.)
is called a state function. This does not depend
on the path used to reach a particular state.
 If the system is changed from one state to another, the
change in a state function is independent of how that
change was brought about.
 Internal energy (U) is a state function. The change in the
internal energy of a system only depends on the amount
of energy in the system at the beginning and the end.
Heat (Q) and Work (W) are not state functions. They
depend on the path of a process.
 Heat and Work

 Heat (Q): the transfer of energy as a result of a

temperature difference.

─ In TD, heat is the name of a process, NOT an entity or

even a form of energy.

─Heat is the transfer of energy by virtue of a

temperature differences.

─ Bodies contain internal energy (U) and not heat.

─ Heat has units of energy (J) and calorie (cal).

1 cal = 4.184 J
 Heat is not a State Function

Raise the temperature of 100 g of water from 25C to 30C.

One way: supply energy as heat by using an electric heater.

1 1
Q  m  Cs  T = 100 g  4.18J  K  g  5K  2kJ

The other way: stir the water vigorously with paddles until 2
kJ of work has been supplied.

Q0

Heat (Q) is not a state function.

 Work is not a State Function
Two different paths between the same initial and final states of an ideal gas

U  0

The gas does no work as

 The gas does work as it expands it expands isothermally
isothermally against an applied, into a vacuum.
matching pressure.
 Because energy flows in as heat
to restore the energy lost as work, Work (W) is not a state
the temperature remains constant.
function.
Note:

 1 cal was the energy needed to raise the temperature of

1 g of water by 1C.

endothermic process exothermic process

energy “into” a system energy “out of” a system

Surroundings Surroundings

Energy Energy
System System

Q >0 Q <0
 Heat and Work

 Work: In mechanics, work is the displacement

(d) against a resisting force (F). W = F  d

─ Work can be expansion work (PV), electrical work,

magnetic work etc.

─ Work has units of energy (J).

─ PV work is work that is the result of a volume change

against an external pressure.
 Volume Work

W  F d
= Pex  A  d
 Pex V

When a system expands, it loses energy as work; so,

when V is positive (an expansion), w is negative.

W   Pex V
convert the units to joules use 101.325 J = 1 atm∙L
Free Expansion : Pex  0 (vacuum), W  0
 Sign conventions

Sign When
heat + heat transferred from surroundings to
system (temperature of system often
increases).
- heat transferred from system to
surroundings (temperature of
surroundings often increases).
work + work is done on system
- work is done by system
If a balloon is inflated from 0.100 L to 1.85 L against an
external pressure of 1.00 atm, how much work is done?

Given: V1=0.100 L, V2=1.85 L, P=1.00 atm

Find: w, J

P, V
Concept Plan:
w
w  - P  V
Relationships: 101.3 J = 1 atm L
Solution:
V  V2  V1 w  P  V  1.75 atm  L 
101.3 J
V  1.85 L - 0.100 L  1.00 atm   1.75 L 
1 atm  L
 1.75 atm  L  - 177 J
 1.75 L
Check:
the unit and sign are correct
2. The First Law of Thermodynamics

In many processes, the internal energy changes

as a result of both work and heat.

l Q
U1 U
W 2
Pex U2 = U1 + Q + W

U  Q  W
Q: heat flow in to the system is positive
heat flow out of the system is negative

W: work done on the system is positive

work done by the system is negative
Note:
 The only way to change the internal energy of
a closed system is to transfer energy into it as
heat or as work.

 If the system is isolated, the internal energy

cannot change at all.

The first law of thermodynamics: The internal

energy of an isolated system is constant.
1. An automobile engine does 520 kJ of work and loses
220 kJ of energy as heat. What is the change in the
internal energy of the engine? Treat the engine, fuel, and
exhaust gases as a closed system.

-740. kJ

2. A system was heated by using 300 J of heat, yet it was

found that its internal energy decreased by -150 J (so  U
= 150 J). Calculate w. Was work done on the system or did
the system do work?

-450 J，system do work

3. Enthalpy and the Enthalpy of Chemical Change

What is the energy change during chemical reactions?

 Most chemical reactions take place in containers open to

the atmosphere and therefore take place at a constant
pressure of about 1 atm.
 Such systems are free to expand or contract. If a gas is
evolved, work is done, even though there is no actual
piston.
 We need another state function, which will allow us to
keep track of energy changes at constant pressure by
taking into account automatically losses of energy as
expansion work.
 Enthalpy

Enthalpy (H), is an extensive property of a

substance that can be used to obtain the heat
absorbed or evolved in a chemical reaction.

H  U  PV
At constant pressure and with no nonexpansion work.

H  U  PV
 Q  W  PV
 Q  Pex  V  PV
 Qp
Note:
 H 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, or independent of path.

 An extensive property is one that depends on the

quantity of substance. H do not have a absolute value.

 A change in the enthalpy (H) of a system is equal to the

heat released or absorbed at constant pressure.

 Usually H and U are similar in value, the difference is

largest for reactions that produce or use large quantities
of gas.

 For an ideal gas, PV = nRT,

H  U  nRT , H  U  nRT
 Endothermic and Exothermic Reactions

endothermic reactions exothermic reactions

Surroundings Surroundings

Heat Heat
System System

H >0 H <0

For an endothermic process, H >0; for an

exothermic process, H <0.
4. Thermochemical Equations

 Reaction enthalpy: The change in enthalpy for

a reaction at a given temperature and pressure.

 Thermochemical equation: The chemical

equation for a reaction (including phase labels)
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
1. In a thermochemical equation it is important to note
phase labels because the enthalpy change, H, depends
on the phase of the substances.

2H 2 (g )  O 2 (g )  2H 2O(g ) ; H  - 483.7 kJ
o

2H 2 (g )  O 2 (g )  2H 2O(l ) ; H  - 571.7 kJ
o

2. When reaction is multiplied by a factor, H is multiplied

by that factor.
C(s) + O2(g) → CO2(g) H = -393.5 kJ
2 C(s) + 2 O2(g) → 2 CO2(g) H = 2(-393.5 kJ) = 787.0 kJ

3. If a reaction is reversed, then the sign of H is reversed.

CO2(g) → C(s) + O2(g) H = +393.5 kJ
H2(g) + 1/2 O2(g) --> H2O(g)
∆H˚ = -242 kJ
2 H2(g) + O2(g) --> 2 H2O(g)
∆H˚ = -484 kJ
H2O(g) ---> H2(g) + 1/2 O2(g)
∆H˚ = +242 kJ
H2(g) + 1/2 O2(g) --> H2O(liquid)
∆H˚ = -286 kJ
 Hess’s Law
4. If a reaction can be expressed as a series of steps, then
the H for the overall reaction is the sum of the heats of
reaction for each step.
 S(s )  O 2 (g )  SO 2 (g ); H o  -297 kJ
2SO 3 (g )  2SO 2 (g )  O 2 (g ); H o  198 kJ
• Could you use these data to obtain the enthalpy change
for the following reaction?

2S(s )  3O 2 (g )  2SO 3 (g ); H o  ?
If we multiply the first equation by 2 and reverse the
second equation, they will sum together to become the
third.

2S(s )  2O 2 (g )  2SO 2 (g ); H o  (-297 kJ)  (2)

2SO 2 (g )  O 2 (g )  2SO 3 (g ); H  (198 kJ)  (-1)
o

2S(s )  3O 2 ( g )  2SO 3 ( g ); H o  -792 kJ

 Sample
Given the following information:
2 NO(g) + O2(g)  2 NO2(g) H° = -173 kJ
2 N2(g) + 5 O2(g) + 2 H2O(l)  4 HNO3(aq) H° = -255 kJ
N2(g) + O2(g)  2 NO(g) H° = +181 kJ
Calculate the H° for the reaction below:
3 NO2(g) + H2O(l)  2 HNO3(aq) + NO(g) H° = ?

[2 NO2(g)  32 NO(g) + 1.5

[3 O2(g)]
O2(g)] x 1.5 H° = (+259.5
1.5(+173kJ)
kJ)
[1
[2 N2(g) + 2.5
5 OO 2(g)
2(g) + +2 1HH 4 2HNO
2O(l)
2O(l) HNO x 0.5 H° = (-128
3(aq)]
3(aq)] kJ)kJ)
0.5(-255
[2 NO(g)  N2(g) + O2(g)] H° = -181 kJ
3 NO2(g) + H2O(l)  2 HNO3(aq) + NO(g) H° = - 49 kJ
 Standard State

The standard state is the state of a material at a

defined set of conditions:
─ pure gas at exactly 1 atm pressure
─ pure solid or liquid in its most stable form at
exactly 1 atm pressure and temperature of
interest
• usually 25°C
─ substance in a solution with concentration 1 M
 H and Hf 

The standard enthalpy change, H, is the

enthalpy change when all reactants and products
are in their standard states.

CH 4 ( g )  2O2 ( g )  CO2 ( g )  H 2O(l ) H  -890kJ

The value signifies that the heat

output is 890 kJ when 1 mol
CH4(g) as pure methane gas at 1
bar is allowed to react with pure
oxygen gas at 1 bar, giving pure
carbon dioxide gas and pure
liquid water, both at 1 bar.
 H and Hf 

 The standard enthalpy of formation, Hf,

(“delta H zero” or “delta H naught”) 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.

─ the elements must be their most stable form in their

standard states.
─ the Hf for a pure element in its standard state = 0
kJ/mol by definition.
 Writing Formation Reactions
Write the formation reaction for CO(g)
 The formation reaction is the reaction between the
elements in the compound, which are C and O.
C + O → CO(g)

 The elements must be in their standard state.

 There are several forms of solid C, but the one with
Hf° = 0 is graphite.
 Oxygen’s standard state is the diatomic gas.
C(s, graphite) + O2(g) → CO(g)

 The equation must be balanced, but the coefficient of

the product compound must be 1.
 Use whatever coefficient in front of the reactants is
necessary to make the atoms on both sides equal
without changing the product coefficient.
C(s, graphite) + ½ O2(g) → CO(g)
C ( gra)  C (diamond ) H  1.9kJ
 Calculating Standard Enthalpy Change for a
Reaction

The enthalpy of a reaction is equal to the total

formation energy of the products minus that of
the reactants.

H 0   nH f 0 (products)   mH f 0 (reactants)

 is the mathematical symbol

meaning “the sum of”;
m and n are the coefficients of the
substances in the chemical equation.
 Example

4 NH3 ( g )  5O2 ( g )  4 NO( g )  6 H 2O  g 
H 0

4( 45.9) 5(0) 4(90.3) 6( 241.8)

H 0  4H f 0 ( NO, g )  6H f 0 ( H 2O, g )

 [4H f 0 ( NH 3 , g )  5H f 0 (O2 , g )]

H o  [4(90.3)  6( 241.8)] kJ  [4( 45.9)  5(0)] kJ

H  906 kJ
o