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Thermodynamics - Lecture notes 1

Chemistry (University of Oxford)

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Tuesday, 10 December 2019

Thermodynamics

- Thermodynamic properties are found to vary with:

Pressure, p p = p(n, V, T)

Volume, V V = V(p, n, T)

Temperature, T T = T(p, V, n)

Amount of substance, n n = n(p, V, T)

• These 4 variables are related for all substances by an equation of state ↑↑↑
• Just two of the variables are enough to define the state and thermodynamic
properties of a closed single-component system

- Systems and surroundings:

• There are 3 types of system:
- Open (energy and matter exchange with surroundings)
- Closed (energy exchanges with surroundings, but matter does not)
- Isolated (neither energy not matter exchanges with surroundings)

- Heat and work:

• A closed system exchanges energy with its surroundings as heat and work
• Work - moving against a force through a distance (w = F x d)
• Heat - transfer of energy down a temperature gradient
• Work leads to uniform motion; heat leads to chaotic motion in the surroundings
• By convention:
w > 0 if work is done on the system

w < 0 if work is done by the system

q > 0 if heat is transferred to the system

q < 0 if heat is transferred from the system

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Tuesday, 10 December 2019

- The First Law: “the internal energy of an isolated system is constant”
• Heat and work change a system’s internal energy:
ΔU = q + w
• Internal energy is a state function (U depends on the state V, T of the system,
not how the system was prepared)
∂U ∂U ∂ ∂U ∂ ∂U
U(V, T ) = (
∂V )T ( ∂T )V ∂T ( ∂V ) ∂V ( ∂T )
dV + dT ∴ ≡

• Internal energy is the sum of the kinetic and potential energies in the system
- It is more powerful to think consider infinitesimal changes of state:
dU = dq + dw
• dU is an exact differential (changes in U between one state Vi, Ti and another
Vf, Tf are given by:
Vf , Tf

∫V , T
ΔU = dU
i i

Vf Tf
= [u] = U(Vf , Tf ) − U(Vi Ti )
V i Tf

• dq and dw are inexact differentials

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Tuesday, 10 December 2019

Expansion work:

- The work done by a gas as it expands and drives the atmosphere back
- Work is NOT a state function (wrev ≠ wirrev)
- General expression comes from physics:

dw = − F dz where dz is distance moved by the object

(the negative sign states that when the system is moving an object against an
opposing force, the internal energy of the system doing work will decrease)

- Free expansion:
• Expansion against zero opposing force (i.e. when pex = 0)
• According to dw = − pex dV, dw = 0 so overall w = 0 and no work is done

- Expansion against constant pressure:

• There is a constant external pressure (i.e. the piston may be pressed on by the
atmosphere, which exerts the same pressure throughout the expansion)

• To find work done:

Vf

∫V
w=− pex dV
i

taking the pex outside and evaluating:

w = − pex(Vf − Vi ) where (Vf − Vi ) is ∆V

∴ w = − pexΔV

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Tuesday, 10 December 2019

- Reversible expansion:
• Reversible - a change that can be reversed by an infinitesimal change in a
variable (Le Chatelier principle)

• To achieve reversible expansion, pex = p − dp at each stage of the expansion.

(pex = p + dp is for contraction). dp is infinitesimally > 0, so can be ignored:

dw = − pex dV = − p dV
This can be integrated and evaluated to find w

- Isothermal, reversible expansion:

• Isothermal - kept at the same temperature
• The equation of state of a gas is pV = n RT
n RT
- Because the expansion is reversible, p = at each stage
V
- T is constant (isothermal), as well as n and R
- Work can be calculated by:
Vf Vf
∫V
dV
w = − n RT = − n RT ln( )
i
V V i

- If the final volume is greater than initial, the logarithm is positive and w > 0.
The system has done work on the surroundings and the internal energy of the
system has decreased as a result of the work it has done

- Reversible vs irreversible expansion:

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Tuesday, 10 December 2019

Heat transactions

- In general, the change in internal energy of a system is:

dU = dq + dwexpansion + dw′extra′

• If a system is kept at constant volume (dwexp = 0) and no extra work is done

(dwe = 0), then:

dU = dqV (subscript V means changes take place at constant V)

- Heat capacity:
• Heat is NOT a state function
• If a gas is in a container of fixed volume (dV = 0), the internal energy can be
plotted against temperature:

• Heat capacities are extensive properties (depends on the amount of matter).

The molar heat capacity at constant volume CV,m is the heat capacity per mole
of material and is an intensive property. Specific heat capacity is the heat
capacity divided by the mass in grams

• Heat capacity is used to relate change in internal energy with change in

temperature at a constant volume (dV = 0):

dU = CV dT
If the heat capacity is independent of temperature over a large range, it is
true to say:

ΔU = CV ΔT
because a change in internal energy can be identified with the heat supplied
at constant volume (dV = 0), it is also true to say:

qV = CV ΔT

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Tuesday, 10 December 2019

Enthalpy

- The change in internal energy is not equal to the heat supplied when the system
is free to change its volume. Some of the energy supplied as heat is returned to
the surroundings as expansion work, so dU < dq
- When heat is supplied at constant pressure, this is equal to the change in
enthalpy of the system:

H = U + pV
• U, p and V are all state functions, so H is too
• “The change in enthalpy is equal to the heat supplied at constant pressure
(provided the system does no additional work)”

d H = dq
so for a measurable change,

ΔH = qp

- The enthalpy of a perfect gas is related to its internal energy by using pV = n RT

in the definition of H:

H = U + pV = U + n RT
This implies that a change in enthalpy in a reaction produces or consumes
gas:

ΔH = ΔU + Δng RT

- Variation of enthalpy with temperature

• Enthalpy increases as temperature increases, but this depends on the
conditions i.e. constant volume/pressure

• The most important condition is constant pressure. The slope of a tangent of a

plot of H against T at constant P gives the heat capacity at constant
pressure, Cp (extensive property). It is analogous to heat capacity at constant V

• Heat capacity at constant pressure is used to relate change in enthalpy with

change in temperature at a constant pressure (dp = 0):

d H = Cp dT

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Tuesday, 10 December 2019

If the heat capacity is constant over a range of temperatures, it is
true to say:

ΔH = Cp ΔT
because a change in enthalpy can be equated with the heat supplied at
constant pressure (dp = 0), it is also true to say:

qp = Cp ΔT

• The variation of heat capacity with temperature can be ignored if the

temperature range is small (this is a very accurate approximation for monatomic
perfect gases)

- Relation between heat capacities

• Most systems expand when heated at constant pressure, and do work to the
surroundings. Some of the energy supplied to them escapes back to the
surroundings. As a result the temperature rises less than when the heating
occurs at constant volume

• A smaller increase in temperature implies a large heat capacity, so in most

cases the heat capacity at constant pressure is larger than its heat capacity at
constant volume

• This simple equation relates the two heat capacities of a perfect gas:
Cp − CV = n R

- Enthalpies of transition:

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Tuesday, 10 December 2019

Entropy

- The Second Law - a spontaneous process in an isolated system is accompanied

by an increase in entropy
dqrev
- dS ≥
T
dqrev
where dS = dSrev and the equality implies a reversible process: dS =
T
- Justification:
• Adding heat to a system increases its disorder and the reversibility requirement
ensures that no extraneous disorder is introduced

• dqrev is an inexact differential, but 1/T is an integrating factor which makes

dqrev
dS = exact and therefore S a state function
T

- Demonstration that ∮ dS = 0

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