Thermodynamics

Content
The Laws of Thermodynamics:
1st Law: conservation of energy, heat Capacity, enthalpy, thermochemistry
2nd Law: Entropy, free energy, chemical equilibrium, fundamental property
relations, Maxwell’s relations.
Solutions and solubility: properties of water, quantifying ionic solubility; acidity, pH
and buffers; gas solubility and Henry’s Law.
Rates of reaction: empirical rate laws, mass action and rates of fundamental steps;
effects of temperature, transition state theory; enzyme-catalysed reactions.
Steady state diffusion: Brownian motion, Fick’s Laws, average diffusion distances.
Reading
Main text: J.M. Seddon & J.D. Gale Thermodynamics and statistical mechanics
Royal Society of Chemistry, Cambridge, 2001
Supplementary reading
C. Lawrence, A. Rodger, R. Compton Foundations of Physical Chemistry Oxford
Chemistry Primer 40, OUP 1996
G. Price Thermodynamics of chemical processes Oxford Chemistry Primer 56,
OUP, 1998.
K.J. Laidler & J.H. Meiser Physical Chemistry 3rd edition, Houghton Mifflin 1999.
K.A. Dill & S. Bromberg Molecular Driving Forces 2nd edition 2011
E.B. Smith Basic Physical Chemistry Imperial College Press 2012
Study groups

Five study group sessions covering: (i) Introduction and first law of
thermodynamics (ii) second law, Gibbs energy, Maxwell’s relations (iii)
solubility and pH (iv) chemical kinetics and enzymes (v) steady state
diffusion.

Prepare fully-worked answers in advance. Be prepared to present your

solutions. Attendance is monitored. Participation is monitored.

The study groups take place in the weeks commencing: 30th Jan, 13th Feb,
27th Feb, 6th March, 20th March.
 Origins in the steam engine
(Clausius, Clapeyron, Carnot...)

Applicability to chemical
systems due to J.W. Gibbs,
E.A. Guggenheim, G.N.
Lewis
“If mathematical analysis should ever hold a prominent place in chemistry- an
aberration which is happily almost impossible- it would occasion a rapid and
widespread degeneration of that science”
Auguste Comte, 1830

Thermodynamics is universal and never wrong

 Thermodynamics in biology & medicine
Define biopolymer structure and stability

Understand binding, adsorption,

biocompatibility (chemical equilibrium,
adsorption, surface energy).
The relationship between free energy and
equilibrium constant is of central importance.
Arrhenius Equation- the link to kinetics

 E 
k  A exp   a 
 RT 

Ea
ln k  ln A 
RT

Even complex chemical reactions have rate

determining steps
 What we’ll be doing
Thermodynamics: energy and mass flows between the system and its
surroundings

“…a spine-chilling story of endless lectures with almost three hundred numbered equations, all of which, it
appeared, had to be committed to memory and reproduced in exactly the same form in subsequent
examinations. Not only did these equations contain all the normal algebraic symbols, but in addition, they
were liberally sprinkled with stars, daggers, and circles so as to stretch even the most powerful of minds”
E.B. Smith

OR: the first two laws and a little calculus

What are the energetic changes associated with chemical reactions? The links
between energy and equilibrium. Gas solubility, ionic solubility and ionisation
(especially pH), electrical potential (batteries, membrane potentials), surface
energy, phase formation…
Chemical kinetics

How rapidly to chemical reactions take place? What are the effects of temperature
and concentration?

Relevance to pharmacokinetics (drug uptake, distribution, metabolism, excretion),

enzymes and their applications, temperature receptors (!)).

Diffusion

How can Brownian motion lead to net material flux? What drives diffusion? What
is its molecular basis?
 What you already know
Energy, work, force, pressure: the Gas Constant R (8.314 J K mol-1), the constant
of proportionality that relates the energy scale in physics to the temperature scale.

The thermal energy a system possesses is around RT Joule. This is the

benchmark.

Molecules and atoms really exist. What is the evidence for this being true?

The mole concept: how many atoms there are in 12 g of 12C? As many starts as
there are in the whole universe.

Everyday objects contain unimaginably large numbers of particles. The mole scales
atomic masses to reasonable units.

Balanced chemical equations: the must be equal numbers of atoms of each

element on both sides.
Chemical equilibrium, ionic equilibrium, law of mass action:

For a reaction: ni moles of reactant Ri in equilibrium with mi moles of product:

𝑛1 𝑅1 + 𝑛2 𝑅2 + ⋯ 𝑛3 𝑅𝑖 ⇌ 𝑚1 𝑃1 + 𝑚2 𝑃2 + ⋯ 𝑚3 𝑃3

At equilibrium the reaction quotient defines the composition and is the equilibrium constant K, which can
be written down by inspection:

𝑃1 𝑚1 𝑃2 𝑚2 … 𝑃𝑖 𝑚3
𝐾=
𝑅1 𝑛1 𝑅2 𝑛2 … 𝑅𝑖 𝑛3

ni and mi are the stoichiometric numbers required to ensure the equation in balanced. Square brackets
are concentrations.

Equilibrium concepts applies to all fundamental steps of all molecular processes: conventional reactions,
gases dissolving in liquids, drugs binding to receptors, molecules partitioning between phases.

Increasing the concentration on one or more Ri drives will increase the concentrations of the products to
maintain K at the same value, and vice versa.
 Some revision and definitions

CONCENTRATION- the amount of solute per unit volume of solution. The

number of particles per unit volume will dictate their energy and their probability
of encountering another molecule: energetics and rates of reaction depend on
concentration.
𝑎𝑚𝑜𝑢𝑛𝑡
𝐶𝑜𝑛𝑐𝑒𝑛𝑡𝑟𝑎𝑡𝑖𝑜𝑛 =
𝑣𝑜𝑙𝑢𝑚𝑒

Amount is usually measured in mole, volume in dm 3 to give mol dm-3. Working in

SI units requires mol m-3.
Common units of concentration:

(i) mol dm-3. Litre is not SI. Decimetre, dm is more explicitly related to m 3, the SI unit. Also known as
molarity.
(ii) Molal: moles per kg of solution
(iii) %(w/w) weight of solute per weight of solution expressed as a percentage (parts per hundred).
(iv) ppm, parts per million: weight of solute.
Can you do concentration calculations?
1. Isotonic saline is 0.15 mol dm -3 NaCl in water. Convert this into SI units.

2. Ethanol has a relative molecular mass of 46.07. English beer is typically 4% (v/v). Approximate this as
exactly 4 g per 100 cm3 of beer. What is the molarity of this beer?

3. The median fasting blood glucose level of a healthy young person is around 5 mmol dm-3. How much
glucose should I weigh to make 50 cm 3 of 5 mmol dm-3 glucose solution? The RMM of glucose is 180.16.

4. MicroRNA is involved in switching genes on and off. A typical single-stranded microRNA might have a
molecular mass of 7500 g mol-1. There needs to be at least 100 molecules per cell for them to have an
effect. What is the approximate molar concentration? The concentration added to cell culture is typically 5
nM. How many molecules in the cell if the cell contents were the same concentration? A typical human cell
is 10 m in diameter. Avagadro’s number is 6.022141  1023.
The perfect gas: pV  nRT
The energy of one mole of a perfect gas depends only on its temperature. The
molecules of a perfect gas take up no space. In a mixture of gases, each gas
behaves as though it was alone.

This equation is sufficiently precise for most situations encountered in

biomedical engineering. Additional terms can be added to allow for different
classes of intermolecular forces at higher pressures.

The “concentration” of a gas, the number of moles per unit volume, = 𝑝Τ𝑅𝑇. So at
constant temperature, partial pressure (the pressure of any one gaseous
component serves the role of concentration.

pV = nRT is used to model dilute solutions, since particles of solute are far apart
on average and otherwise act randomly.
 Key concepts in thermodynamics: energy
Energy comes in two flavours: HEAT & WORK q + w

HEAT FLOW: transfer of energy due to a temperature difference between a system and its surroundings
WORK: a process which could be used directly to move an object a certain distance against an opposing
force.
w   Fds
Types of Work
Extension, f .dl Volume, -pext .dV
Surface, .d Electrical, .dq

Political/ philosophical definition

Two types of work (Bertrand Russell): (i) Movement of an object at or near the Earth’s surface from one location
to another (ii) Supervising such operations. (i) is unpleasant and poorly paid, (ii) is well-paid and pleasant.
 Key concepts in thermodynamics: systems
Thermodynamics divides the whole universe into two parts:
(i) The system: that part of the universe we’re interested in
(ii) The surroundings: the rest of the universe. Remain at constant T, p

It is concerned with the exchange of energy and matter between the system and its surroundings.

Energy comes in two forms: (i) heat, or chaotic energy e.g. Brownian motion (ii) work, e.g. expansion (pV work),
creating surfaces, electrical work

Systems are classified according to the constraints on energy and matter exchange

Energy The system Matter

OPEN System
 Key concepts in thermodynamics: systems
Thermodynamics divides the whole universe into two parts:
(i) The system: that part of the universe we’re interested in
(ii) The surroundings: the rest of the universe. Remain at constant T, p

It is concerned with the exchange of energy and matter between the system and
its surroundings.
Energy comes in two forms: (i) heat, or chaotic energy e.g. Brownian motion (ii)
work, e.g. expansion (pV work), creating surfaces, electrical work
Systems are classified according to the constraints on energy and matter
exchange

Energy X The system X Matter

ISOLATED System
 Key concepts in thermodynamics: systems
Thermodynamics divides the whole universe into two parts:
(i) The system: that part of the universe we’re interested in
(ii) The surroundings: the rest of the universe. Remain at constant T, p

It is concerned with the exchange of energy and matter between the system and
its surroundings.
Energy comes in two forms: (i) heat, or chaotic energy e.g. Brownian motion (ii)
work, e.g. expansion (pV work), creating surfaces, electrical work
Systems are classified according to the constraints on energy and matter
exchange

Energy The system

X Matter

CLOSED System, only energy exchange

 Key concepts in thermodynamics: systems
Thermodynamics divides the whole universe into two parts:
(i) The system: that part of the universe we’re interested in
(ii) The surroundings: the rest of the universe. Remain at constant T, p

It is concerned with the exchange of energy and matter between the system and
its surroundings.
Energy comes in two forms: (i) heat, or chaotic energy e.g. Brownian motion (ii)
work, e.g. expansion (pV work), creating surfaces, electrical work
Systems are classified according to the constraints on energy and matter
exchange

Heat The system X Matter

Work X
ENERGY
Diathermic System- a closed system, only heat exchanged
 Key concepts in thermodynamics: systems
Thermodynamics divides the whole universe into two parts:
(i) The system: that part of the universe we’re interested in
(ii) The surroundings: the rest of the universe. Remain at constant T, p

It is concerned with the exchange of energy and matter between the system and
its surroundings.
Energy comes in two forms: (i) heat, or chaotic energy e.g. Brownian motion (ii)
work, e.g. expansion (pV work), creating surfaces, electrical work
Systems are classified according to the constraints on energy and matter
exchange

Heat
X The system X Matter
Work

ENERGY
Adiabatic System- a closed system, only work exchanged
 Key concepts in thermodynamics: summary
Energy is the sum of heat q and work w.
Consider energy and matter exchanges between our system and its surroundings (which are at constant T and
p).
A system is classified as:
(i) Isolated: neither energy nor matter are exchanged
(ii) Open: both matter and energy can be exchanged with the surroundings.

(iii) Closed: only energy can be exchanged.

(a) adiabatic: only work can be exchanged.
(b) diathermic: only heat be exchanged.
It matters how the energy is exchanged because this affects the maths we can use. If the system is allowed to
be at equilibrium throughout the process, this is reversible and extracts the maximum amount of work.
JARGON
Exergonic- the system gives out energy. Endergonic- the system takes in energy
Exothermic- the system gives out heat. Endothermic- takes in heat

Sign convention We are concerned with the system. Energy taken in by the system is positive, energy given
out is negative.
We are not mechanical engineers
 The laws of thermodynamics (1)
0) There is a unique scale of temperature.
1) The energy of an isolated system is constant.
2) When two systems are brought into thermal contact, heat flows spontaneously from the one at the higher
temperature to the one at the lower temperature.
OR
2) Heat cannot be completely converted into work for any cyclic process, but work can be completely
converted into heat.
OR
Spontaneous changes are always accompanied by a conversion of energy into a more disordered form.
OR
The entropy, S, of an isolated system increases during any spontaneous change or process.

3) All perfect materials have the same entropy at absolute zero. For T > 0, S > 0, it is impossible to cool any
system to T = 0
From first and second law, four Gibbs equations can be derived. From the Gibbs equations > 50,000,000
equations can be rigorously derived.
 The laws of thermodynamics (2)
1) You can’t win, you can only break even.
2) You can only break even when it’s very cold.
3) It never gets that cold.
 Some revision and definitions (1)
States of Matter
(i) GAS

BEHAVIOUR MODEL
Fills the container it Is composed of widely
occupies separated particles in
continuous rapid disordered
motion. Each particle
travels several diameters
before colliding with
another particle. The
particles only interact
weakly
 Some revision and definitions (2)
States of Matter
(ii) LIQUID

BEHAVIOUR MODEL
A fluid that possesses a Is composed of particles in
well-defined surface. In a contact but able to move.
gravitational field it fills the Particles can only travel a
lower part of its container. fraction of a diameter
before a collision occurs.
 Some revision and definitions (3)
States of Matter
(iii) SOLID

BEHAVIOUR MODEL
Retains its shape. Particles are in contact &
unable to move past each
other. Particles oscillate
around an average location
but are essentially trapped
and frequently lie in more
or less ordered arrays
 Some revision and definitions (3)
PHYSICAL STATE: The condition of a sample of stuff
in terms of physical form (gas, liquid, solid), V, T, p,
amount, n.
FORCE: A body travels in a straight line at constant
speed unless acted on by a force. F = ma. Measured
in newton, N.
WORK: Force  distance

w   Fds
 Some revision and definitions (4)
F
PRESSURE: Force per unit area: p
A

Can arise from numerous collisions of gas molecules

Units of pressure pascal, Pa, N m-2;
atmosphere, atm; mmHg; bar; lbf in-2. SI unit is pascal, Pa

pascal atm mmHg bar lbf in-2

1 Pa 1 9.869  10-6 7.501  10-3 10-5 1.450  10-4

1 atm 1.013  105 1 760 1.013 14.70
1 mmHg 133.3 1.316  10-3 1 1.333  10-3 1.934  10-2
1 bar 105 0.9869 750.1 1 14.50
1 lbf in-2 6895 6.805  10-2 51.71 6.895 10-2 1
 Some revision and definitions (5)
TEMPERATURE, T: That property which determines the direction of energy
flow.
T/ K = / C + 273.15
VOLUME, V: the space occupied by a system, is an extensive property and a
state function.
ENERGY: Capacity to do work, measured in joule, J. There are 2 contributions
to the total energy of a collection of particles:

Kinetic Energy, Ek  1 mv2

2
Potential Energy, E p  mgh
Total energy  Ek  E p
 Some revision and definitions (6)

AMOUNT OF STUFF: Mass (kg) is independent of identity. However if we study

ensembles of particles, mole is the appropriate unit.
1 mol is the number of particles in exactly 12 g of 12C.
NA = 6.022141  1023
MOLAR MASS, M: mass per mol of substance, e.g. MH2O = 18.02 g mol-1. How
many mol H2O in a litre of H2O?

RMM, relative molecular mass is the atomic or molecular mass relative to 12C.
 Some revision and definitions (7)

EXTENSIVE PROPERTY: depends on amount, e.g. mass, volume.

INTENSIVE PROPERTY: independent of amount e.g. T, p. Some intensive
properties are the ratios of two extensive properties e.g. density, concentration.
SYSTEM: region of chemical interest e.g. cell, body, reaction vessel
characterised by T, p, V, composition.
SURROUNDINGS: That part of the universe which is not the system.
CHEMICAL THERMODYNAMICS
The First Law
Internal energy, U, of a system is the total energy it contains as a results of its
physical state (T, p, V, n etc.). U is a constant unless changed by work, w or
heat, q.

U  w  q

U is a state function, path independent and an extensive property, though

molar internal energy, Um = U/ n is intensive.
U is the probability-weighted sum of the energy levels of atoms or molecules
making up the system.
Types of work
(i) Expansion of gas against a constant pressure:

Vf

w  p(V )dV
Vi
Vf

  pext  dV
Vi

  pext (V f  Vin )

  pext V
Types of work (cont.)
(ii) Isothermal reversible expansion
Adjust pext to be equal to p at each infinitesimal step
Vf

wexp    pext (V )dV

Vi

For an ideal gas, pV = nRT

Vf
dV
 wexp  nRT V V
i

Vf 
 wexp  nRT ln  
 Vi 
Types of work (cont.)
(iii) Irreversible expansion: instantaneously lower pext from pA to pB. The
expansion occurs against constant external pressure, pB.

wexp   pB V

(true for either adiabatic or isothermal expansion)

 wexp (irr )  wexp (rev )

nRT
pA p
V

pB
wirr

VA VB
It is clear that work is not a state function. The heat transfer is different for the
two different paths,  q is not a state function either.

dU  q  w

dU is an EXACT DIFFERENTIAL i.e.:

 U   U 
dU    dx    dy
 x  y  y  x

where x, y are any two of p, V, T

Digression (1) State functions, partial differentials, exact differentials

The state of a perfect gas is defined by specifying p, V and T.

Since pV = nRT, specifying and 2 of p, V and T for a fixed mass fixes the remaining variable. An equation
such as T = f(p, V) is called an equation of state.

U is different from q and w in that it only depends on the state of the system. If we fix, e.g., p and T, then U
has a definite value. U, like p, T and V is a state function and does not depend on the path followed (like
latitude and longitude).

(i)If a state function is integrated:

B
U   dU
A

The integral has a definite value which is independent of the path taken
between A and B. dU is an exact differential.
 (ii) We can write an exact differential
If internal energy U is a function of T and p:

U  f (T , V )
 U   U 
dU    dT    dV
 T V  V T

These are called partial derivatives. They are evaluated by treating one variable as a constant. The
subscript says which one is fixed.

(iii) The order of differentiation does not affect the result.

We’ll be using these important properties in connection with the second law.
Partial differentiation, exact differentials and Maxwell’s
relations

Any function f(x,y) of two variables will have a gradient in all directions in the x, y
plane. First consider the simple cases of finding the rate of change of f(x,y) in the
positive x and y directions. These rates of change are the partial derivatives
with respect to x and y respectively and written as:

 f   f  The subscript shows which variable is kept

  and   constant, and treated as a constant as in
 x  y  y  x “normal” differentiation.

Higher differentials are defined in an analogous way:

  f   2 f   f   2 f   f   2 f   f   2 f
  2    2     
x  x  x y  y  y x  y  xy y  x  yx
Provided the second partial derivatives are continuous at the point in question,
the following useful relationship always holds:

2 f 2 f and this is generally true for n variable functions


xy yx
Worked examples
Find the first and second derivatives w.r.t. x and y of the functions f(x,y) (i) = x2y (ii)
r(x,y,z) = (x2 + y2 + z2)1/2
f f 2 f 2 f
(i)  2 xy  x2  2x  2x
x y xy yx

r x x
 
 
(ii) and similarly for y
x r x2  y2  z 2
1/ 2

 2 r   x  1 x  r  y 2  z 2 and similarly for second

    2  
x 2
x  r  r r  x  r3 derivative w.r.t. y

 2r   y xy  2r   x xy
   3    3
xy x  r  r yx y  r  r
Quantifying heat changes
Molar heat capacity is the amount of energy required to
raise 1 mol by 1 K. Specific heat capacity is referred to 1 g.

q  nCm T

More strictly:
 dq 
C  
 dT 

q is the heat, n is the number of moles, Cm is the molar

heat capacity, T is the temperature change
1. Estimate the rise in temperature in the water falling over the Niagara Falls.
The height of the falls is 50 m. The heat capacity of 1 mol of water (0.018 kg)
is 80 J K-1. The acceleration due to gravity is 9.8 m s-2.

2. An electric kettle operating at 250 V and 8 A holds 1 kg of water. The initial

temperature is 300 K, calculate how long it takes to reach the boiling point,
373 K. The heat capacity of water is 4200 J K-1 kg-1. Assume the heat
capacity does not vary with temperature and that there are no thermal losses.
Quantifying heat changes (2)- getting serious

(i) Isochoric heat capacity (constant volume), Cv

If dV = 0, the system does no work.
 dU  dq V
 U 
 CV   
 T V
(ii) Isobaric heat capacity (constant pressure), Cp
dU  dq  pext dV This looks messy, but suggests that if heat
 dq  dU  pext dV transfer is confined to processes where only
 U  pext dV  pV work is done, then it can be defined in
C p   
 T p terms of state functions.

U is usually less for constant pressure processes

However, Cp does depends on temperature. Generally expressed as a power
series for practical purposes:

C p  a  bT  cT 2  dT 3
ENTHALPY, H
dH = (q)p if there is no work other than pV work, and:

H  (q) p

Giving the definition of enthalpy as:

H  U  pV

 H 
C p   
 T  p
ENTHALPY (cont)
H is therefore a STATE FUNCTION allowing its application to thermochemistry.
Note: if heat is released in a reaction, it is exothermic and H is negative. If heat is absorbed, the reaction is
endothermic and H is positive.

The integral of dH therefore yield an exact value.

HESS’S LAW
The total enthalpy change for a reaction is independent of reaction path. More
usefully, the standard enthalpy of a reaction is the sum of the standard enthalpies
of of the individual reactions into which the reaction may be divided.
Standard T: 25C, 298.15 K
Standard p: 1 bar, 105 Pa
Standard state: Pure component at 1 bar
Hess’s Law exploits the property of state functions- the change in value does not
depend on the path taken. Tabulated values of enthalpies of formation of
molecules from their atoms are widely available. The elements are assumed to
already exist and therefore have enthalpies of formation of zero. A path (usually
just conceptual) exists from reactants  products via the atoms of the elements.

Hr Since H is a state function, Hr

Reactants Products must have the same value going
the hypothetical path via the
atoms as directly.
-Hf (reactants) Hf (products)

∴ ∆𝐻𝑓 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 − ∆𝐻𝑓 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠 = ∆𝐻𝑟

Atoms
Obviously, the numbers of atoms of each element must be the same for the
reactants and products, i.e the equations must be balanced.
 ENTHALPY (cont.)
for the reaction: aA + bB  cC + dD

  
H ro  cH of ,C  dH of , D  aH of , A  bH of , B 
Generally:

H ro  
Products
Prod H of ,Prod  
Reactants
React H of ,React

Enthalpies of formation of many compounds are available in tabulated

compilations, defined per mol of compound.
By convention, enthalpies of formation of the elements are zero.
The standard enthalpy of combustion of sucrose (C12H22O11) to form gaseous
CO2 and liquid H2O is
-5647 kJ mol-1 at 25 C. What is the standard molar enthalpy of formation of
sucrose at 25 C? The standard enthalpy of formation of CO2 is –393.5 kJ mol-1,
and that of H2O(l) is –285.8 kJ mol-1.
 Temperature dependence of H- Kirchhoff’s Equation

 H 
Cp   
 T  p
T2 This only works because all the
  dH   C p dT variable are state functions
T1

One useful form of this equation is:

H of ,T  H 298
o
 C p T  298.15
where C p is the mean heat capacity over the temperature range.

If the heat capacity does change, then:

H 2  H1  C p T2  T1 
Example
The enthalpy change H when one mole of water freezes at 273 is -6.00 kJ.
Cp for water is 75.3 J K-1 mol and for ice is 37.6 J K mol-1. Calculate the
enthalpy change when water freezes at 253 K

H 2  H1  C p T2  T1 
H 2  H1  C p T2  T1 
H 2  6000  (37.6  75.3)( 253  273)
H 2  6000  754  5.2 kJ

Thus endeth the first law