Thermodynamics

Dr. Aashani Tillekaratne

M.Sc. Chemistry Education
2022
1
❖Study of transformations of energy

❖Energy output of chemical reactions

❖How energy flows in biological cells

❖How large molecules assemble into complex

structures like the cell

2
 First law of thermodynamics
Energy determines:
❖ what molecules can form
❖ what reactions can occur
❖ how fast they can occur
❖ in which direction a reaction has a tendency to occur

In biology, we come across many examples of the relationship

between energy and work.

❖ contraction and relaxation of muscles

❖ movement of nutrients and ions across membranes
❖ synthesis of biological molecules
❖ cell division
3
 First law of thermodynamics
A statement of the law of conservation of energy.

Energy can be neither created nor

destroyed but merely converted from
one form into another or moved from
place to place.

dU = δq + δw (differential form)

ΔU = q + w (integrated form)

4
 Vocabulary of thermodynamics
❖System and surroundings

❖Types of systems
Open
Closed
Isolated

❖Work and heat

❖Internal energy
❖Enthalpy
❖Entropy
❖Gibbs energy
❖Helmholtz energy 5
 Work and heat
❖Energy can be exchanged between a closed system and
its surroundings by doing work or by “heating”

❖If the system does work, it can be used to change the

height of a weight somewhere in the surroundings

❖“Heating” is the process of transferring energy as a

result of a temperature difference between system and
surroundings

❖Work and heat are modes of transfer of energy.

6
Diathermic wall Adiabatic wall

cold hot
hot cold

7
Different ways of transferring energy
3
( NH 2 ) 2 CO( s) + O2 ( g ) → CO2 ( g ) + 2 H 2O(l ) + N 2 ( g )
2

CO2 (g) + N2 (g)

3/2 O2 (g)

(NH2)2CO (s)
H2O(l)

8
 Measurement of work
❖If the force is the gravitational attraction of the earth on a mass
m, the force opposing raising the mass vertically is mg (g =
acceleration of free fall = 9.81 ms-2)

❖Work needed to raise the mass through a height h on the surface

of the earth is mgh.

❖To measure the work done by or on a system, we measure the

height through which a weight is raised or lowered in the
surroundings and then use the above relation.

9
 Measurement of work
Nutrients in the soil are absorbed by the root system of a tree
and then rise to reach the leaves through a complex vascular
system in its trunk and branches. What is the amount of work
required to raise 10 ml of liquid water through the trunk of a
20 m tree from its roots to its topmost leaves?

10
Sign convention in thermodynamics
w <0 q<0
ENERGY

ENERGY
WORK HEAT

w>0 q>0
ENERGY

ENERGY
WORK HEAT

11
 Internal energy
❖Internal energy, U, of a system is the sum of all the
kinetic and potential contributions to the energy of all
the atoms, ions and molecules in the system.

❖It is an extensive property.

❖We measure changes in internal energy (ΔU).

ΔU = q + w (integrated form)

w = energy transferred by doing work

q = energy transferred by heating 12

 Internal energy - Example

Nutritionists are interested in the use of energy by the

human body, and we can consider our own body as a
thermodynamic “system”. Suppose in the course of an
experiment, you do 622 kJ of work on an exercise bicycle
and lose 82 kJ of energy as heat. What is the change in
your internal energy? Disregard any matter lost by
perspiration.
(Note: Keep track of correct signs).

13
An electric battery is charged by supplying 250 kJ of energy
to it as electrical work (by driving an electric current
through it), but in the process it loses 25 kJ of energy as
heat to the surroundings. What is the change in internal
energy of the battery?

14
Internal energy of an isolated system is
constant (1st Law of Thermodynamics)

15
 Enthalpy

❖Most processes (including biological

processes) take place in vessels open to
atmosphere

❖These are subjected to constant pressure; not

constant volume

❖Therefore, we need to learn how to

quantitatively treat the energy exchanges
taken place by heating at constant pressure.

16
 Enthalpy
H = U + PV ΔH = ΔU + Δ(PV)

Δ(PV) = PfVf – PiVi

If the changes occur at constant pressure,

Δ(PV) = PVf – PVi = P(Vf – Vi) = PΔV

At constant pressure:

ΔH = ΔU + PΔV

At constant pressure and if no non-expansion work:

ΔH = qP 17
 Entropy
❖Entropy of an isolated system that is not in
equilibrium will increase until the system reaches
equilibrium.

❖After that, entropy remains constant.

❖Entropy of an isolated system is a maximum when the

system is in equilibrium.

❖dS = 0 for any reversible process in an isolated system

❖dS > 0 for a spontaneous process in an isolated system

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 Entropy
❖One form of the second law:
q
Clausius inequality: S  
T
❖Total entropy change that accompanies a process:

ΔStotal = ΔSsys + ΔSsurr

❖ For a spontaneous change, ΔStotal > 0

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 Entropy
❖For a chemical reaction or a phase transition taking
place at constant pressure:

H
S surr =− (qsys = ΔH and qsurr = -qsys)
T
❖ At constant pressure and temperature:

H
Stotal = S −
T

20
❖We define Gibbs energy as: G = H – TS

❖At constant temperature: ΔG = ΔH - TΔS

H
Stotal = S −
T
❖ At constant pressure and temperature, we get:

G = −TStotal

21
 Therefore, at constant pressure and temperature,
change in Gibbs energy of a system is proportional to
the overall change in entropy of the system plus its
surroundings.

22
 Spontaneity and Gibbs energy
❖For spontaneous changes:

Stotal  0
G  0 (for processes occuring at
constant T and P)
❖ In a spontaneous change, at constant temperature
and pressure, Gibbs energy decreases.

A process is favourable if ΔG < 0

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24
 G = H − TS

ΔH ΔS Thermodynamically
favoured?
Yes. At all temperatures.
- +
No. At all temperatures.
+ -
Depends on T
+ + (entropy driven)
Depends on T
- - (enthalpy driven)

25
 Work and Gibbs energy change
❖Value of ΔG for a process gives the maximum non-
expansion work that can be extracted from the
process at constant T and P.

❖ Non-expansion work (w’) is any work other than

that arises from the expansion of the system.

❖ Combining first and second laws:

G = w' (at constant T and P)
max

❖ Maximum work is done during a reversible change.

Therefore,
G = wrev
'
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 Proof:
At constant temperature: dG = dH – TdS
(‘d’ denotes an infinitesimal change)

At constant pressure: dH = dU + PdV

At constant temperature and pressure:

dG = dU + PdV –TdS

dU = dq + dw (1st Law)

dG = dq + dw + PdV –TdS

Work done on the system consists of expansion work (-PextdV) and non-expansion work (dw’)

dG = dq – PextdV + dw’ + PdV – TdS

For a reversible change: P = Pext and dq = TdS

Therefore, dG = dw’rev (at constant temperature and pressure for a reversible process)
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 Work and Gibbs energy change
If there is any irreversibility in the process, quantity of
work obtained will be less than the maximum.

If ΔG < 0 spontaneous process

and wnon P-V is the maximum work, exclusive of P-V work
that can be obtained from the system.

If ΔG > 0 non-spontaneous process

and wnon P-V is the minimum work, exclusive of P-V work
that has to be done on the system to make the process
happen.
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 Work and Gibbs energy change
Example:
1
𝐻2 𝑔; 1 𝑏𝑎𝑟, 298.15 𝐾 + 𝑂2 (g; 1 bar, 298.15 K)
2

∆𝐺 = −237.1 𝑘𝐽 𝑚𝑜𝑙 −1

𝐻2 𝑂 𝑙; 1 𝑏𝑎𝑟, 298.15 𝐾

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Example:

Suppose a small bird has a mass of 30 g. What is the

minimum mass of glucose that it must consume to fly up
to a branch 10 m above the ground? The change in
Gibbs energy that accompanies the oxidation of 1 mol of
C6H12O6 (s) to CO2 (g) and liquid water at 25 °C is -2828
kJ.

Molar mass of glucose = 180 g mol-1

g = acceleration of free fall = 9.81 ms-2

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Example:

A hardworking human brain operates at about 25 J s-1.

What mass of glucose must be consumed to sustain that
metabolic rate for an hour?

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 Work and Gibbs energy change
❖ If we know ΔG, then we know the maximum non-
expansion work that we can obtain by harnessing the
reaction in some way.

❖ ΔG is an important quantity in studying the

energetics of systems that are not at equilibrium,
such as living systems.

❖ The value of ΔG is an indication of how far from

equilibrium the system is.

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 Predicting the sign of ΔS
Predict whether ΔS is positive or negative for each of the
following processes, assuming each occurs at constant
temperature.

(a) 𝐻2 𝑂 𝑙 → 𝐻2 𝑂 g

(b) 𝐴𝑔+ 𝑎𝑞 + 𝐶𝑙 − 𝑎𝑞 → 𝐴𝑔𝐶𝑙 s

(c) 4𝐹𝑒 𝑠 + 3𝑂2 𝑔 → 2𝐹𝑒2 𝑂3 s
(d) 𝑁2 𝑔 + 𝑂2 𝑔 → 2𝑁𝑂 g

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❖Calculate the entropy change for the
following reactions:

H2 (g) + Cl2 (g) 2HCl (g)

N2 (g) + 3H2 (g) 2NH3 (g)

Species S° (J mol-1 K-1)

H2 (g) 130.7
Cl2 (g) 223.08
N2 (g) 191.5
HCl (g) 186.2
NH3 (g) 192.5
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 Absolute values of entropies
❖ 1st Law - Energy

❖ 2nd Law - Entropy

❖ 3rd Law – provides a numerical scale for entropy

35
 Absolute values of entropies

❖ 1st Law: for a reversible process:

dU = qrev + wrev

❖ 2nd Law: qrev = TdS

❖ and: wrev = − PdV

dU = TdS − PdV

36
❖ It can be shown that:  S  = CV
 
 T V T
❖ This tells how S varies with T at constant V.
Integrate above equation with respect to T
(keeping V constant):
S = S (T2 ) − S (T1 )

T2 CV (T )dT
S =  (constant V)
T1 T

❖ If we know Cv(T) as a function of T, we can

calculate ΔS.
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❖ At constant pressure, similarly:

H = U + PV

dH = dU + PdV + VdP = TdS – PdV + PdV +VdP

dH = TdS + VdP
 S  CP (T )
❖ It can be shown that:   =
 T  P T
S = S (T2 ) − S (T1 )

T2 C P (T )dT
S =  (constant P)
T1 T
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 T2 CP (T )dT
S = S (T2 ) − S (T1 ) =  (constant P)
T1 T

Let T1 = 0 K;
T2 C P (T )dT
S (T2 ) = S (0 K ) +  (constant P)
0 T

What is this S(0 K)?

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 Third Law of Thermodynamics

In a perfectly ordered, pure crystalline substance,

entropy is zero at 0 K.

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Entropy of a system is related to the total number of
possible microscopic states of that system – called
thermodynamic probability (ω or Ω) – by the
Boltzmann relation:

S = kB ln ω
ω = number of ways the total energy of a system may
be distributed over its various energy states

kB = Boltzmann constant

At 0 K system is in its lowest energy state.

ω = 1 and ln ω = ln 1 = 0 and S = 0 41
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43
44
From Third Law:

S (0 K) = 0
T2 C P (T )dT
S (T2 ) = 
0 T
0 K is the lowest possible temperature in the universe.

0 K ≈ -273.15 °C = -459.7 F

In real world, no system can have a temperature of 0 K,

because of the 2nd law.

Entropies reported on the basis that S (0 K) = 0 are

called Third-Law Entropies. 45
 Nernst (unattainability) principle
Any thermodynamic process cannot reach the
temperature of absolute zero by a finite number of
steps and within a finite time.
T2
T2 CP dT
S (T2 ) =  =  CP d ln T
0 T 0

Minimum temperature at which CP can be measured is

15 K.

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 Nernst (unattainability) principle
Debye extrapolation (Debye third power law):

When temperature is low, we can assume that CP α T3

CP = aT3 (a is a constant)

T
15 CP dT 2
S (T2 ) = S (o) +  +  CP d ln T
0 T 15

Area of shaded region

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 T
15 CP dT 2
S (T2 ) = S (o) +  +  CP d ln T
0 T 15

3 T2
15 aT dT 15
S (T2 ) = S (o) +  +  CP d ln T = S (o) +  aT 2 + area
0 T 15
0

3 15
 aT 
S (T2 ) = S (o) +   + area
 3 0
 a153   a153 
S (T2 ) = S (o) +  − 0 + area = S (0) +   + area
 3   3 
CP15K = a153 This can be measured

CP15 K CP15 K
S (T2 ) = S (o) + + area = + area
3 3 48
Question:

According to Debye theory, the low-temperature molar heat

capacity of non-metallic solids goes as,
3
12  T 
4
C P (T ) = R 
 D 
5 0 < T ≤ Tlow

Where, Tlow depends on the particular solid but is about 10 – 20

K for most solids. θD is a constant characteristic of the solid. θD
has units of temperature and is called the Debye temperature of
the solid. Show that, if C P is given by the above expression, the
low-temperature contribution to the molar entropy is given by:

C P (T )
S (T ) = 0 < T ≤ Tlow
3
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 Phase transitions
If there is a phase transition between 0 K and T2, at Ttrans, the
entropy of this phase transition must be added between T = 0 K
to T2.

Example: consider the following sequence of processes for

substance ‘A’ which melts at Tm and boils at Tb.
A (s, 0 K, 1 bar) A (s, Tm, 1 bar) A (l, Tm, 1 bar)

A (l, Tb, 1 bar) A (g, Tb, 1 bar) A (g, T2, 1 bar)

Its entropy at T2 (T2 > Tb) is:

CP ( s)dT  fus H b CP (l )dT  vap H 2 CP ( g )dT
T T
Tm
S (T2 ) = S (o) +  + + + +
0 T Tm Tm
T Tb Tb
T
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 3rd Law - meaning
As the temperature of a system approaches absolute zero, its
entropy approaches a constant. For pure, perfect crystals, this
constant is zero.

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 Gibbs Energy and Equilibrium
 rnG =  rnG  + RT ln Q

 r n G  =  f −
  G
products

 f
  G 

reac tan ts

Q =  aJ J
J

R = 8.314 J mol-1 K-1 T = temperature in Kelvin

Q = reaction quotient

For pure solids and liquids, activity is 1. Such substances make no

contribution to Q. 52
 Gibbs Energy and Equilibrium
 rnG =  r nG  + RT ln Q

This determines ΔG at any composition or temperature

conditions.

At equilibrium, ΔG = 0 and Q = Keq

ΔG° = -RT ln Keq

ΔG° = -RT ln KP (gas phase)

Relative values of Q and K establish the direction that the

reaction takes in coming to equilibrium.
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 Gibbs Energy and Equilibrium
Q < K reaction proceeds as written (to the right)

Q > K reaction proceeds as written, to the left

Q = K equilibrium, ΔG = 0; ΔG°=-RT ln K

If ΔG°rxn> 0, then, K < 1 (reactants are favoured)

If ΔG°rxn< 0, then, K > 1 (products are favoured)

54
 Gibbs Energy and Equilibrium
G  = − RT ln K P

G = − RT ln K P + RT ln QP

Q 
G = RT ln  P 
 KP 

At equilibrium, ΔG = 0 and QP = KP

If QP < KP, then, ΔG < 0 reaction is spontaneous from

left to right as written

QP must increase as the reaction proceeds towards

equilibrium.
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 Temperature dependence of
equilibrium constant
G  = − RT ln K eq

 r n G 
ln K eq = −
RT

K (T2 )  rn H  1 1 
ln =  −  van’t Hoff equation
K (T1 ) R  T1 T2 

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 Partial molar volume (V ) i

•It is the contribution that a componenet of a

mixture makes to the total volume of a sample.

•It is defined as the increase in the volume of an

infinite amount of solution when 1 mol of
component i is added.

 V 
V =  
 n 
i

i p ,T , n j i

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 V = n AVA + nBVB

Partial molar volumes of the components of a mixture

vary with the composition of the mixture, because the
environment of the molecules in the mixture changes
with the composition.

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Class question: A famous example.
When 1 mol of water is added to a large volume of pure
water at 25 ˚C, the volume increases by 18 cm3. However, if
1 mol of water is added to a large volume of pure ethanol,
the volume increases only by 14 cm3.
Explain.

59
Answer:
•In case 1, molar volume of pure water is 18 cm3 mol-1.
•In case 2, partial molar volume of water in pure ethanol is 14
cm3 mol-1.
•The volume occupied by a given number of water molecules
depends upon the identity of the surrounding molecules.
•In case 2, there is so much ethanol present. Each water
molecule is surrounded by ethanol molecules. The packing of
the molecules results in the water molecules increasing the
volume by only 14 cm3.
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Partial molar free energy (G ) i

 G 
  =G =
 n 
i i

i p ,T , n1 , n2

G = n G + n G + .... + n G
1 1 2 2 i i

G = n  + n  + .... + n 
1 1 2 2 i i

61
62
 G = n A G A + nB GB + ......... + ni Gi

 G 
G A =   = A
 n A  P ,T ,nB ,nC ,....

G = nA  A + nB B + ......... + ni i

Chemical potential of a substance, μi is, the change in free

energy of a system when you add 1 mol of substance i to
that system, keeping the temperature, pressure and the
number of moles of any other substances present in the
system. 63
 Chemical potential & Phase equilibria
 G 
Gi =   = i
 ni  P ,T ,n A ,nB ,....
Chemical potential measures the increment of free energy
accompanying an infinitesimal change in the amount of one
particular component in a system.

It is applicable to chemical equilibria and phase equilibria.

Eg: relationship between the chemical potential values of a

substance in different phases of a multi-phase system.
64
If a number of phases are in equilibrium, chemical potential
of a given component will have the same value in all phases
into which that component can pass.

Transfer of an infinitesimal amount of a component between

two phases (α and β) in equilibrium at constant T and P must
involve a zero free energy change.
dG =  i dni
i

dG = i dni + i dni = 0

since dni = − dni ( 

i )
− i dni = 0
This can only be true if:  i =  i
65
 Chemical potential & Concentration
Ideal and non-ideal solutions

There are a number of ways of approaching the definition of

solution ideality.
One way is to define an ideal solution as the one in which the
chemical potential of each component is given by:

i =  + RT ln X i

i

At low concentrations molar concentration is proportional to

mole fraction.
i =  + RT ln ci

i 66
Deviations from ideal behaviour is addressed by introducing
an activity coefficient.

i =  + RT ln  i ci

i

i =  + RT ln ai

i
γi = a function that describes all deviations from ideality
ai = activity (effective concentration)

67
Solute activities and their “real” concentrations

ai =  i mi or ai =  i ci

What do we really mean by “activity” or “apparent

concentration”?

68
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