Chapter 2

The First Law of

Thermodynamics

The Concepts
OUTLINE
Atkin’s
Definitions 2.1
The First Law of Thermodynamics 2.2
Work 2.3
Heat 2.4
Enthalpy 2.5
Adiabatic changes 2.6
Standard enthalpy changes 2.7
Enthalpies of formation 2.8
Temperature dependence of enthalpy changes 2.9

HOMEWORK ASSIGNMENTS
EXERCISES 2.4 - 2.44, Part (a)s only
PROBLEMS 2.2, 2.3, 2.12, 2.13, 2.27
Definitions

THERMODYNAMICS

• Chemical thermodynamics is concerned with the equilibrium

properties of substances or mixtures in so far as they are
effected by temperature.

• Thermodynamics serves two functions:-

1. To decide how some process can be made to occur.

2. If a process is spontaneous it can tell us how much
work we can get from it. If not spontaneous whether it
is worthwhile making the process occur.
Definitions

SYSTEM AND SURROUNDINGS

The system is the part of the universe we are interested in.

The rest of the universe is the surroundings.

Definitions

Classification of systems

If matter and energy can be transferred

between the system and the surroundings then
the system is called _______.

If matter cannot be exchanged with the

surroundings, but energy can be, the system is
called ________.

If neither energy nor matter can be transferred

the system is called ___________.
Definitions

The State of a System

A system is in a definite state when each of its properties

has a definite value.

The state of a system is uniquely defined in terms of a few

state properties that may be linked by an EQUATION OF
STATE.
Definitions
PROPERTIES
The properties of a system are those physical attributes that are
perceived by the senses or are made perceptible by certain
experimental methods of investigation e.g. pressure,
temperature, etc.
A state property (a.k.a. state function, state variable) is one
which has a definite value when the state of the system is
specified.
The properties of a system may be:

INTENSIVE EXTENSIVE
Do not depend on the quantity of matter Do depend on the quantity of matter
Definitions

WORK

Defined in physics as ____  ______ . It represents something

useful. Getting something from one place to another we regard
as useful.

ENERGY

Energy is the capacity of a system to do work.

The more energy a system has the more work it can do.
Mathematically energy and work are interconvertible;
something can be given energy by doing work on it.
Definitions

HEAT

A system may gain or lose energy because of a

temperature difference between it and the
surroundings, we say "energy has been
transferred as heat".

The first law of thermodynamics relates HEAT and

WORK.
Definitions

Forms of energy
Kinetic energy, the energy associated with a moving body.
Potential energy, the energy associated with the position of a
body. Electrical energy, the energy associated with the motion
of electrons. Chemical energy, the energy associated with
chemical bonds. Heat, the kinetic energy of molecular motions.

Internal energy
The energy contained within a system. It is an extensive state
property and given the symbol U.

It is measured in joules, J, where 1 J = 1 kg m2 s-2

Definitions

System enclosures/walls

If a system cannot receive or give energy to the

surroundings in the form of HEAT then it is said to be
contained within an ___________ enclosure.

If a system can receive or give energy to the surroundings

in the form of HEAT then it is said to be contained within a
____________ enclosure.
Definitions
PROCESSES, CHANGES IN STATE and PATHS (1)

A process is said to have occurred if any macroscopic property of

a system changes between 2 observations made on the system.

A change in state is completely defined when initial and final

states of a changed system are specified.

The path specifies the sequence of intermediate states between

the initial and final states.
Definitions
PROCESSES, CHANGES IN STATE and PATHS (2)

Any process that releases heat is called ______________,

e.g. combustion.

Any process that absorbs heat is called ______________,

e.g. evaporation.

A cyclic process (or transformation) is one in which the

initial state and the final state is the same.
THE FIRST LAW OF THERMODYNAMICS

The first law of thermodynamics is essentially the statement of the

principle of the conservation of energy for thermodynamical
systems.

We will investigate the validity of this statement.

First, let U represent the change in a systems internal energy in

going from state A to state B i.e.

U = UB - UA

This change is independent of the path of the change of state.

THE FIRST LAW OF THERMODYNAMICS
A system gaining energy through a thermal process absorbs a
positive quantity of heat.

Let q represent the heat absorbed by the system from the

surroundings.

When the system gains energy by other methods a positive

quantity of work is done on the system.

Let w represent the work done on the system by the

surroundings.

For a change of state from A to B the first law states:

U = UB - UA = q + w
Work and the First Law

In order to use the first law in a practical way it is convenient to

switch to infinitesimal changes.

dU = dq + dw

We know that: Work = Force  Distance. Therefore:

dw = F dz

If the object moves from zi to zf, the total work done is

zf

w   Fdz
zi
Work and the First Law

1. A system raises a mass m by a distance h. What is w?

w = -mgh.

2. The system contains a spring which is compressed by a

distance x from the equilibrium position, zi = 0. What is w?

The force law (Hooke's Law) is

F = -kz (k is the FORCE CONSTANT)

so dw = kz dz
zf


w  kz dz  1/ 2 kz 
2 x
0 1/ 2 kx 2
zi
Work and the First Law
In many cases found in chemistry work is done by the system
when it expands against an external pressure.

Consider an expansion:
dw = -F dz

= -pexA dz

= -pexdV
Vf

w  p
Vi
ex dV

For a compression dV < 0 and thus dw > 0.

FREE EXPANSION: pex= 0 and w = 0.
Work and the First Law

Types of changes:

If the system is kept continually in a state of equilibrium while a

change is carried out then that process is called REVERSIBLE.

Example: Compressing a gas in a cylinder (the system) by pushing

in the piston very slowly.

Truly reversible processes are ideal: they are carried out infinitely
slowly and will be capable of doing the maximum amount of work.

If the piston were pushed in fast the gas near the piston would heat
up and/or currents would form and the system would no longer be in
equilibrium. This would be an IRREVERSIBLE process.
Work and the First Law

Types of changes:

If pex = p we have equilibrium. If we

increase pex infinitesimally the gas contracts
slightly and vice versa. In either case the
pex change is reversible.

If pex >> p then decreasing pex infinitesimally

will not cause the gas to stop contracting and
p vise versa. Here infinitesimal changes in
conditions do not cause opposite changes in the
state of the system. The system is not in eqm
with its surroundings and the change described
is irreversible
Work and the First Law

Consider the reversible, isothermal expansion of 1 mol of ideal gas.

Reversible, so p = pex = nRT/V.

dw = -pdV = -nRT/V dV
Vf
nRT  Vi 
w   dV nRT ln  
V V 
Vi  f
This is all of the area under the
curve in the indicator diagram.
Irreversible: Allow pex < p then V
increases instantly from Vi to Vf.
The work is less.
Max work performed is -wrev.
 Work and the First Law
Q. What is w when 56 g of Fe(s) reacts with HCl(aq) to give H2(g)
(a) At fixed volume?
(b) In an open beaker?
Work and the First Law

From Atkins 2.7 (b): 2 mol of He is expanded isothermally at

22oC from 22.8 L to 31.7 L

(a) Reversibly
(b) Against constant pex equal to final pressure of the gas
(c) In a vacuum.

For the 3 processes calc. w.

Work and the First Law

Expansion/compression work is called "pV work”and in this

context the First Law becomes

dU = dq + dw = dq - pdV

Constant volume conditions (Heat and the First Law)

dU = dqV ( dqV = dq at constant V ) and dV = 0

so U = U2 - U1 = qV.

The heat withdrawn from the surroundings by a constant-volume

system is equal to the change of internal energy of the system.
Measuring U: Adiabatic Bomb Calorimeter

In practice we use a
sealed CALORIMETER
and measure heat
changes at constant
volume (qV).
 Calorimetry
The calorimeter directly yields U (via qV ).

Again: dU = dqV+dw

= dqV - pexdV
0 (V is constant)
= dqV
U = qV

Step (1) Set up exp’t and wait for eqm. Measure bath
temperature, T. Perform reaction. Measure rise in T ( = T ).

Step (2) Cool contents of calorimeter back to T. Do electrical

work on the water + bomb to reproduce T. Apply first law.
Heat and the First Law – Heat Capacities

The heat capacity, C, of any system is the amount of heat required

To raise the temperature of the system by 1 K.

Define: dq
C
dT
It is useful to distinguish heat capacities at constant volume
and constant pressure.

 dq   U   dq   U   V 
CV     ; C p  dT   T   p T 
 dT  V  T  V p p p

Lets derive these…

Constant pressure conditions
Often chemical systems are studied at constant external pressure.

This makes it difficult to measure changes in U.

We invent a convenience function, H, the ENTHALPY, defined by:

H = U + pV

At constant pressure its use is seen from:

dH = dU + pdV + Vdp

dH = dU – dw = dqp

so qP = H2 - H1 = H.
H is the heat transfer at constant pressure.
Constant pressure conditions

Notes about H:

(i) H is an extensive state property.

(ii) Even for non-constant p, H has a definite value.

However, in such a case H  q

(iii) For processes involving solids and liquids H  U

usually.
Constant pressure conditions

Self test 2.3 from Atkins:

Calculate the difference between H and U when 1.0 mol of grey tin (density
= 5.75 g cm-3) changes to white tin (density 7.31 g cm-3) at 10.0 bar. At 298 K,
H = +2.1 kJ.
Constant pressure conditions

In the reaction 2H2(g) + O2(g) →2H2O(l), 3 mol of gas phase molecules

is replaced by 2 mol of liquid phase molecules. Calculate the difference
between the enthalpy and the energy taking place in this system.
(T=298 K, assume perfect gas behaviour).
 The Variation of Enthalpy with Temperature.

A few slides earlier we introduced:

 dq   U   dq   U   V 
CV     and C p      p 
 dT V  T V  dT  p  T  p  T  p

But recall:
dH = dU – dw = dqp

So it follows that:
 dq   dH 
C p    
 dT  p  dT  p

And so at constant pressure: dH= CpdT

The relation between Cp and CV

If something is heated at constant p we generally observe an expansion.

So the system receives energy in the form of heat but loses energy in
the form of pV work. Therefore the temp. rises less than when heating
at constant volume.

The rate of change of temp. w.r.t. heat is less at constant p than at

constant V.

Recall that C is a measure of the rate of change of the systems heat

w.r.t. temperature.
dq
C
dT

So, if the temp. of a system rises slower at constant p compared to

constant V, then it follows that: Cp > CV
The relation between Cp and CV
We will show now and in a later lecture that:

Cp-CV = nR

It may be shown by kinetic theory that

CV,m=(3/2)R for a monatomic gas

CV,m=(5/2)R for a diatomic gas

Hence:
Cp,m=(5/2)R for a monatomic gas
Cp,m=(7/2)R for a diatomic gas

C p ,m CV ,m  R R
If we put:    1
CV ,m CV ,m CV ,m

 = (5/3) for a monatomic gas

 = (7/5) for a diatomic gas
The Adiabatic Expansion of a Perfect Gas

The change of a thermodynamical system is said to be adiabatic if it is

reversible and if the system is insulated so that no heat can be exchanged
between it and its environment during the change.

“Expansion”  work is done by the system on the surroundings.

“Adiabatic enclosure”  no heat exchanged, q = 0

 First Law tells us U will be < 0 and that it will equal wad
 The Adiabatic Expansion of a Perfect Gas

 U 
Under constant volume conditions: CV  
 T V

dU
For a perfect gas U depends only on T and so we may write: CV 
dT

So the change in internal energy is U = wad = CV(Tf-Ti)

The work done during an adiabatic expansion of a perfect gas is

proportional to the difference of the initial and final temperatures.

c
For a reversible adiabatic  Tf   Vi  C
expansion of a perfect gas ln   ln   ; c  V
V 
we may derive:  Ti   f nR
The Adiabatic Expansion of a Perfect Gas

Using the Heat Capacity Ratio,  , we can address the change in pressure
that accompanies an adiabatic reversible expansion of a perfect gas

C p ,m CV ,m  R R
Recall:   1
CV ,m CV ,m CV ,m

We can show that

pV  constant

( c.f. the equation pV = constant for an isothermal expansion )

A practical example of adiabatic expansion/contraction

If a body of air in the atmosphere changes height, the pressure and

hence volume change, leading to a temperature change.
Let pressure be p at a height h. Molar mass = M = 0.029 kg mol-1,
g = acceleration due to gravity = 9.81 m s-2.

In the atmosphere, dp/dh = -pMg/RT.

What is dT/dh ?

This is called the DRY ADIABATIC LAPSE RATE.

Thermochemistry

Thermochemistry is the quantitative study of the heat produced

by a given chemical reaction.
If we perform this reaction:

HCl(aq) + NaOH(aq) → NaCl(aq) + H2O(l)

We will note that the vessel gets hot.

Alternatively, if we perform the following reaction in a beaker:

Ba(OH)2∙8H2O(s) + 2NH4NO3(s) → Ba(NO3)2(s) + 2NH3 (aq) + 10H2O(l)

We will observe the spontaneous formation of ice on the outside of the

vessel as the temperature of the system decreases rapidly.
Thermochemistry

It is more convenient to measure enthalpy changes, H,

(constant pressure) as opposed to internal energy changes,
U, (constant volume).
Lets not lose sight of:
H is an extensive state property.

H = U + pV With the absorbtion of heat, q,

we get an increase in enthalpy,
dH = dU – dw = dqp i.e. H > 0 and the process is
called endothermic. If H < 0
the process is exothermic.
 dq   dH 
C p    
 dT p  dT p

And so at constant pressure: dH= CpdT

Thermochemistry

We don’t (can’t) measure a chemical’s enthalpy. What we measure is the

change in enthalpy that occurs during a transformation.

In order to report enthalpy changes, H, for a given transformation it is

useful to discuss changes between substances in their standard states, we
then use H to represent the standard change in enthalpy.

The standard state of a substance at a specified temperature

is its pure form at 1 bar.

E.g. the standard state of oxygen at 298.15 K is pure O 2(g), ethanol at

158 K is pure C2H5OH(s), C at 298.15 K is pure C(graphite).
Thermochemistry

There are many enthalpies of transition. Some examples are:

H2O(l) → H2O(g) enthalpy of vaporization, vap H

Reactants → Products enthalpy of reaction, r H

Elements  Compound enthalpy of formation, f H

Species (s, l, g)  Atoms (g) enthalpy of atomization, at H

See Atkin’s Table 2.4

 Thermochemistry
Hess's Law

Consider: 1?
C2H2(g) + H2(g) C2H4(g)

2 3
2 CO2(g) + 2 H2O(l)

“The standard enthalpy, Hө, of an overall chemical reaction is the

sum of the standard enthalpies of the individual reactions into
which a reaction may divided”.

We can set up Hess cycles to calculate H for reactions which

are difficult to measure directly.

In the above cyclec Hө2 – c Hө3 = r Hө1

Thermochemistry
Consider:

Hydrogenation of propene,

CH2=CHCH3(g) + H2(g)  CH3CH2CH3(g) r Hө = -124 kJ mol-1

Combustion of propane,

CH3CH2CH3(g) + 5 O2(g)  3 CO2(g) + 4 H2O(l) c Hө = -2220 kJ mol-1

Formation of water,

H2(g) + 0.5 O2(g)  H2O(l) f Hө = -286 kJ mol-1

Calculate c Hө for CH2=CHCH3(g)

Thermochemistry
The reaction enthalpy in terms of enthalpies of formation
Taking Hess’s law to its logical conclusion suggests that we may consider a
reaction as proceeding by first breaking the reactants up into its elements and
then forming the products from those elements.
Elements
Enthalpy, H

-f Hө
+f Hө
Reactants r Hө

 r H θ  f H θ (products)   f H θ (reactants) Products

  f 
 
products
H θ
 f (If all stoichiometric no's  ve)
  H
reactants
θ

 b  f H θ (If stoichiometric no' s  ve for products, - ve for reactants)

b
Thermochemistry
At 298 K: 0.5 H2(g) + 0.5 I2(s)  HI (g) f Hө = 26.98 kJ mol-1
H2(g) + 0.5 O2(g)  H2O (g) f Hө = -241.82 kJ mol-1

Determine r Hө and r Uө for

4 HI(g) + O2(g)  2 I2(s) + 2 H2O(g) (Assume the gases behave perfectly)

4 [0.5 H2(g) + 0.5 I2(s)] + O2(g)

Enthalpy, H

-f Hө
+f Hө
4 HI (g) + O2 (g) r Hө

2 I2(s) + 2 H2O(g)

 r H θ  b  f H θ 2 f H θ (H 2 O)  4 f H θ (HI) = -591.6 kJ mol-1

b
Thermochemistry
The dependence of r H on T: Kirchoff’s law
 dq   dH 
We know: C p     ; dH= CpdT
 dT  p  dT  p
Heating a substance from T1 to T2 its enthalpy changes from H (T1) to:
T2

H (T2 )  H (T1 )  C p dT
T1

This applies to each substance in the reaction, therefore:

T2

 r H θ (T2 )  r H θ (T1 )   r C θp dT
T1

 r H θ (T1 )  (T2  T1 ) r C θp
where  r C θp  bC θp ,m
b
Thermochemistry
The dependence of r H on T: Kirchoff’s law

Example 2.7:

At 298 K : H2(g) + 0.5 O2(g)  H2O (g) f Hө = -241.82 kJ mol-1

Given:

Cp,m / J K-1 mol-1

H2O (g) 33.58
H2 (g) 28.84
O2 (g) 29.37

What is f Hө at 100oC? (Assume all heat capacities, Cp,m , are independent of T)

Chapter 2 SUMMARY
1. Systems may be open, closed or isolated.
2. Definitions of work, internal energy (U) and work. First
Law: or dU = dq + dw.
3. U, and enthalpy, H, are state functions. H = U + pV.
4. pV work and reversible/irreversible volume changes for an
ideal gas at constant volume or pressure.
5. Calorimetry and the measurement of H and U.
6. Thermochemistry: Hess's Law, thermochemical cycles and
standard enthalpies of formation.
7. The heat capacities Cp and CV: relation to temperature
dependence of H and U for a process (Kirchoff's Law) and
for adiabatic changes.