Chapter 2

The basis of chemical

thermodynamics
Cai Zheng
School of pharmacy
Thermodynamics

• How much of chemical reaction energy will be transferred or

converted?

• Can a reaction occur spontaneously at a given condition?

Table of content

• Thermodynamic system

• Energy conservation and heat of chemical reaction

• Entropy and Gibbs’s free energy

2.1 Thermodynamic system
Thermodynamic system: large number of particles in macroscopic space.

Thermodynamic system
2.1.1 System and its surroundings

system
surrounding
universe
Three types of system
exchange mass energy
Opening system √ √
Closed system × √
Isolated system × ×
 2.1.2 State functions

 The state of one particle has 6 parameters.

 The state of a system is described by them in a microstate.
 The microstate changes with time.
 A macrostate of a system is described by its macroscopic (collective)
properties.
Macroscopic physical quantities are state functions.
Typical state functions: p, V, T etc

at equilibrium not at equilibrium

Energy and mass are distributed in a system.

A system is internal thermodynamic equilibrium if there is no macroscopic

energy or mass flow within it.
2.1.3 heat and work

A closed system changes from one state to another state by exchanging

energy with its surrounding.

The forms of energy exchange are work(W) and heat(Q).

Work and heat path functions(depending on the path of change).

Work: energy transferred to or form the system through change of ordered
motion of particles.

Pressure-volume(pV) work:

1970 IUPAC work done by the system on the surroundings is negative W<0

work done by the surroundings on the system is positive W>0

Heat: energy transferred at the result of temperature difference, to or form the
system through change of disordered motion of particles.

1970 IUPAC released heat from the system is negative Q<0

absorbed heat by the system is positive Q>0

Heat and work are not state functions.

Heat and work are equivalent.

Drop
hammer
Paddle
wheel
2.2 Conservation of Energy and Heat of Chemical Reaction

2.2.1 Thermodynamic Energy and the First Law of Thermodynamic

 Internal energy(U) is the energy of the entire system. Including the

chemical, translational, vibrational, rotational and interactional energies.

 Impossible to determine the absolute value

 State function

 Unit J
The First Law of Thermodynamic

∆ 𝑈 =𝑄 +𝑊 Conservation of energy

For ex.
2.2.2 Enthalpy Change and Isobar Heat
Different process of heat
Constant volume
State 1 State 2

The state of a system changes from state1 to state 2 through constant volume
process, without any other of work

∆ 𝑈 =𝑄 V
 isobar process
State 1 State 2

The state of a system changes from state1 to state 2 through isobar process without any
other of work except volume work
∆ 𝐻 =𝑄 p
enthalpy (H) state function unit J

Enthalpy change is the heat of isobaric process.

The real value of enthalpy of a system can’t be measured.

Experimental measurement of Qp is easy and precise with a thermometer.

Most of chemical reactions occur at constant pressure with volume work only.

Product must be at the same temperature as the reactant when the heat effect is

measured.
For a reaction

aA(g) + bB(g) dD(g) + eE(g)

At different reaction condition, the heat is different.

The different

= +Δn(RT)

=ΔU+Δn(RT)

Δn=(d+e)-(a+b) Δn=0 =
ΔV=0 solid or liquid state
Exercise

Calculate the heat effect on the constant pressure at 298 K.

(1) 2H2S(g)+SO2(g) 2H2O(l)+3S(s) QV=-223.8 kJ

(2) 2C(gra.)+ SO2(g) 2CO(g)+S(s) QV=-231.3 kJ

(3) H2(g)+Cl2(g) 2HCl(g) QV=-184 kJ

An endothermic process is a process in which the system receives heat is
positive(Q>0)
In an isochoric endothermic process(

In an isobaric endothermic process(), the enthalpy increases.

An exothermic process is a process in which the system releases heat is

negative(Q<0).
In an isochoric exothermic process( the internal energy decreases

In an isobaric exothermic process(), the enthalpy decreases.

Thermo-chemical equation

/mol
The standard enthalpy of reaction (ΔrH Θ) is the total molar enthalpy change in
a system during a chemical reaction, when all reactants and products are in
their standard states.

aA(g) + bB(g) dD(g) +eE(g) Δr H Θ

The matter state of substances should be denoted ： s l g aq

Standard state pΘ=100 kPa, cΘ=1 mol/L

 A thermo-chemical equation can reveal the relationship between the

reaction and heat signed by ΔrHΘ exchange with the surroundings.

at 298.15 K

H2(g) + 1/2O2(g) H2O(g) ΔrH Θ =-285.8 kJ/mol

2H2(g) + O2(g) 2H2O(g) ΔrH Θ =-571.6 kJ/mol

H2O(g) H2(g) + 1/2O2(g) ΔrH Θ =+285.8 kJ/mol

Hess’s law

Hess’s law is natural as enthalpy is a state function.

 Sample problem 2-2

(1) C(gra.) + O2(g) CO2(g) ΔrHm,1Θ =-393.5 kJ/mol

(2) CO(g) + 1/2O2(g) CO2(g) ΔrHm,2Θ =-282.99 kJ/mol

How much is the Δ rHm,3Θ of the reaction (3) C(gra) + 1/2O2(g) CO(g)
Sample problem 2-3

(1) Fe2O3(s) + 3CO(g) 2Fe(s)+3CO2(g) ΔrHm ， 1Θ =-26.7 kJ/mol

(2) CO(g) + 1/2O2(g) CO2(g) Δ rHm ， 2Θ =-283.0kJ/mol

Calculate the value of Δ rHm ， 3Θ for the reaction (3)

(3) 2Fe(s) +3/2 O2(g) ) Fe2O3(s)
2.3 Entropy and Gibbs’s free energy

2.3.1 Spontaneous process

A system occurs naturally without any drive from the surroundings.

The general characteristics of these spontaneous processes can be
summarized:

• Tend to proceed in unidirection, the adverse direction cannot take place without

energy supplied by the outside work.

• Can do work on the surroundings.

• Lead to an equilibrium state in the end.

 2.3.2 Entropy of a system

 The interpretation of entropy in statistical mechanics is the measure of

disorder.
 Isolated system has higher probability to become more disordered over time
(increase of entropy).
Entropy S unit: J/K
State function

ΔrS =S2-S1

The entropy change in reaction

ΔrS Θ= (products)─ (reactants)

Compare the entropy of the same substance

 S(s)<S(l)<S(g)

 S(low temp.)<S(high temp.)

 S(higher pressure)<S(lower pressure)

 When molecules are mixed, entropy increases.

 During a reaction which increases of the number of molecules, entropy

usually increases.
exercise

Predict the sign of entropy change for each of the following reactions:

（ Pa,298K) Pa,298K)

（ 2 ） NH4Cl(s) NH3(g)+HCl(g)

（ 3 ） CO(g)+H2O(g) CO2(g)+H2(g)
2.3.3 Gibbs’s free energy of system

Constant temperature and constant pressure

State function G
Relate three functions: H S T ∆ 𝐺=∆ 𝐻 − 𝑇 ∆ 𝑆

 0 spontaneously process
 0 at equilibrium
 0 non-spontaneously process
 The spontaneity of a process is discussed

 < 0 and 0, < 0 spontaneously at any temperature

 > 0 and < 0, > 0 not occur
 < 0 and < 0, < 0 spontaneously at low temperature
 > 0 and > 0, < 0 spontaneously at high temperature
 Calculate ΔrG Θ Unit kJ/mol

ΔrG Θ= (products)─ (reactants)

∆ r G   Θ=∆ r H  Θ −𝑇 ∆ r S   Θ

At non-standard

aA(aq) + bB(aq) dD(aq) +eE(aq)

ΔrG = ΔrG Θ +RT lnJ ( c / 𝑐⊖ ) 𝑑 ( c / 𝑐⊖ )𝑒

𝐽=
( c / 𝑐⊖ )𝑎 ( c / 𝑐 ⊖ )𝑏
Given the following reactions

(1) 4NO(g) 2N2O(g)+O2(g) Δr =-139.56 kJ/mol

(2) 2NO(g) + O2(g) 2NO2(g) Δr =-69.70 kJ/mol

Calculate Δr for the reaction of 2N2O(g)+3O2(g) ) 4NO2(g)

Summary

 State functions: U H S G

 Hess’s law

 Two forms of energy transfer: work and heat

 The first law of thermodynamics

 The direction of spontaneous reaction

Exercise

(1) C(diamond) +O2(g) CO2(g) ΔrHm ， 1Θ =-395.4 kJ/mol

(2) C(graphite) + O2(g) CO2(g) ΔrHm ， 2Θ =-393.5 kJ/mol

Calculate the value of Δ rHm ， 3Θ for the reaction (3)

(3) C(graphite) C(diamond)