1

TOPIC 5
THERMOCHEMISTRY
5.2 Hesss Law

5.2 Hesss Law

2

Start

Finish

A State Function: Path independent.

Both lines accomplished the same result,
they went from start to finish.
Net result = same.

Hess Law Defined

Enthalpy is a state function. As such, DH for going

from some initial state to some final state is pathway
independent.
Hess Law:
The enthalpy change, DH for a chemical reaction is
independent of the route by which of the chemical
reaction occur.
DH for the overall equation is the sum of the DHs for
the individual equations: DHrxn = DH1 + DH2 +

Hess Law
4

Example :
Two ways:
1. A B C
2. A C

Enthalpy change: H3 = H1 + H2
What ever route we going to take , the H is same.

Hess Law
5

Example :

H3 = H1 + H2
-1646kJmol-1 = H1 + (-1367kJmol-1)
H1 = -279kJmol-1

Using Hess Law

Example: Calculate the enthalpy of reaction, DHrxn, for the
formation of nitrogen monoxide from its elements
N2 + O2 2NO
DHrxn = ?

Using these equations:

4NH3 + 3O2 2N2 + 6H2O

DH = -1530 kJ

(1)

4NH3 + 5O2 4NO + 6H2O DH = -1170 kJ

(2)

Using Hess Law

7

4NH3 + 3O2 2N2 + 6H2O

DH = -1530 kJ

4NH3 + 5O2 4NO + 6H2O DH = -1170 kJ

(1) flip
(2)

2N2 + 6H2O 4NH3 + 3O2

DH = +1530 kJ

(3)

2N2 + 2O2 4NO

DH = +360 kJ

N2 + O2 2NO

DH =+180 kJ

Using Hess Law

N2 (g) + 2O2 (g)

2NO2 (g)

2NO2 (g)

q
N2 (g) + 2O2 (g)

When calculating DH for

a chemical reaction as a
single step, we can use
combinations of reactions
as pathways to
determine DH for our
single step reaction.

Exp 1 :
Determine the heat of reaction for the reaction:
4NH3(g) + 5O2(g)

4NO(g) + 6H2O(g)

Using the following sets of reactions:

N2(g) + O2(g) 2NO(g)

DH = 180.6 kJ

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

DH = -91.8 kJ

2H2(g) + O2(g) 2H2O(g)

DH = -483.7 kJ

Hint: The three reactions must be algebraically

manipulated to sum up to the desired reaction.
and.. the DH values must be treated accordingly.
9

Goal:

4NH3(g) + 5O2(g)

4NO(g) + 6H2O(g)

Using the following sets of reactions:

N2(g) + O2(g) 2NO(g)

DH = 180.6 kJ

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

DH = -91.8 kJ

2H2(g) +
NH3:
O2 :

O2(g) 2H2O(g)

DH = -483.7 kJ

Reverse and x 2 4NH3 2N2 + 6H2 DH = +183.6 kJ

Found in more than one place, SKIP IT (its hard).

NO: x2
H2O: x3

2N2 + 2O2 4NO

6H2 + 3O2 6H2O

DH = 361.2 kJ
DH = -1451.1 kJ
10

Goal:

4NH3(g) + 5O2(g)

4NO(g) + 6H2O(g)

NH3: Reverse and x2 4NH3 2N2 + 6H2 DH = +183.6 kJ

O2 : Found in more than one place, SKIP IT.
NO: x2
2N2 + 2O2 4NO
DH = 361.2 kJ
H2O: x3
6H2 + 3O2 6H2O
DH = -1451.1 kJ

Cancel terms and take sum.

4NH3

+ 5O2

4NO

+ 6H2O

DH = -906.3 kJ

Is the reaction endothermic or exothermic?

11

Exp 2:
Determine the heat of reaction for the reaction:
C2H4(g) + H2(g) C2H6(g)
Use the following reactions:
C2H4(g) + 3O2(g) 2CO2(g) + 2H2O(l)

DH = -1401 kJ

C2H6(g) + 7/2O2(g) 2CO2(g) + 3H2O(l)

DH = -1550 kJ

H2(g) +

1/2O2(g) H2O(l)

DH = -286 kJ

12

Exp 2 :
Determine the heat of reaction for the reaction:
Goal: C2H4(g) + H2(g) C2H6(g)

DH = ?

Use the following reactions:

C2H4(g) + 3O2(g) 2CO2(g) + 2H2O(l)

DH = -1401 kJ

C2H6(g) + 7/2O2(g) 2CO2(g) + 3H2O(l)

DH = -1550 kJ

H2(g) + 1/2O2(g) H2O(l)

DH = -286 kJ

C2H4(g) :use 1 as is C2H4(g) + 3O2(g) 2CO2(g) + 2H2O(l) DH = -1401 kJ

H2(g) :# 3 as is
H2(g) + 1/2O2(g) H2O(l)
DH = -286 kJ
C2H6(g) : rev #2
2CO2(g) + 3H2O(l) C2H6(g) + 7/2O2(g) DH = +1550 kJ
C2H4(g) + H2(g) C2H6(g)

DH = -137 kJ
13

HESS LAW

Another way of thinking about Hess Law is

graphically in terms of energy cycles.
The enthalpy change for a reaction depends only on
the difference between the enthalpy of the products
and the enthalpy of the reactants. It is independent
of the reaction pathway.

HESS LAW
The enthalpy change going from A to B is the same
whether the reaction proceeds directly to A or
whether it goes via an intermediate.

A
DH1

DH2

C
DH3

DH1 = DH2 + DH3

HESS LAW

This law is simply a statement of the law of

conservation of energy.
It can be used to determine enthalpy changes
which cannot be measured directly.

HESS LAW
For example, the enthalpy of combustion of both carbon and
carbon monoxide to form carbon dioxide can easily be measured
directly, but the combustion of carbon to carbon monoxide cannot.
This can be represented by an energy cycle.

C(s) + O2(g)
-393
O2(g)
-1
kJ mol

CO2(g)

DHx

CO(g)
O2(g)

-283 kJ mol-1

-393 = DHx + (-283), DHx = -393 + 283 = -110 kJ mol-1

Example: Calculate the standard enthalpy change when one mole of methane is
formed from its elements in their standard states. The standard enthalpies of
combustion ( DHc) of carbon, hydrogen and methane are -393, -286 and -890 kJ
mol-1 respectively.

Step 1: Write the equation for enthalpy change with the

unknown DH value. Call this value DHx.

C(s)

2H2(g)

DHx

CH4(g)

Example: Calculate the standard enthalpy change when one mole of methane is
formed from its elements in their standard states. The standard enthalpies of
combustion ( DHc) of carbon, hydrogen and methane are -393, -286 and -890 kJ
mol-1 respectively.

Step 2: Construct an energy cycle showing the different

routes to the products (in this case the products of
combustion).

C(s)

O2(g)
CO2(g) +

2H2(g)
O2(g)
2H2O(g)

DHx

CH4(g)
2O2(g)

Example: Calculate the standard enthalpy change when one mole of

methane is formed from its elements in their standard states. The standard

enthalpies of combustion (DH c ) of carbon, hydrogen and methane are 393, -286 and -890 kJ mol-1 respectively.

Step 3: Use Hess Law to equate the energy changes for the
two different routes.

C(s)

O2(g)
CO2(g) +

2H2(g)
O2(g)

DHx

CH4(g)
2O2(g)

2H2O(g)

DHc (C) 2DHc (H2 ) DHx DHc (CH4 )

direct route

route via methane

Example: Calculate the standard enthalpy change when one mole of methane is
formed from its elements in their standard states. The standard enthalpies of
combustion ( DHc) of carbon, hydrogen and methane are -393, -286 and -890
kJ mol-1 respectively.

Step 4: Rearrange the equation and substitute values to

solve for the unknown DH value.

DH (C) 2DH (H2 ) DH

DH (CH4 )

DHx DHc (C) 2DHc (H2 ) DHc (CH4 )

DHx 393 2(-286) - (-890)
DHx 75 kJmol-1

Verification of Hesss Law

DH = enthalpy change
Route 1

NaOH (s)

Route 2

NaOH (s)

DH 2

DH 1

+ H2O (l)

NaCl (aq)
NaCl (aq)
+ HCl aq)

DH 3

NaOH (aq)
The conversion of solid NaOH to sodium chloride solution can be
achieved by two possible routes. One is a direct,single-step process,
(adding HCl (aq) directly to the solid NaOH) and secondly a two-step
process (dissolve the solid NaOH in water first, then add the
HCl(aq)) All steps are exothermic.
If Hesss Law applies, the enthalpy change for route 1 must be the same
for the
DH 1 = DH 2 + DH 3 overall change for route 2.

Experimental Confirmation of Hesss Law

Route 1 DH 1
50 ml 1mol l-1 HCl

Route 2 DH 2

+ DH 3

50 ml H2O

50 ml HCl

then
2.50g of KOH added to a dry, insulated
beaker.
Before adding the acid, its temperature
is recorded. The final temperature rise
after adding the acid is also recorded.
Knowing the specific heat capacity for
water, it is then possible to calculate the
Enthaply change for this reaction.

1. 2.50g of KOH added to a dry, insulated

beaker.
2. Before adding the water, its temperature
is recorded. The final temperature rise
after adding the water is also recorded.
3. Now add the acid, again, recording the final
temperature rise.

DH 2

DH 3

DH2
DH 1 = c m DT
and DH 3 DH = c m DT
DH 2 + DH 3 = DH 1 will verify Hesss law
Use the equation below to calculate

Combining Equations

DH c H = -286 kJ mol
DH c C= -394 kJ mol

Hesss law can be used to calculate enthalpy changes that

cannot be directly measured by experiment.
Route 1
3C (s) + 3H2 (g)
Route 1 cannot be carried out
C3H6 (g)
in a lab, as Carbon and
Hydrogen will not combine
Route 2a
Route 2b
directly.
3CO2 (g) + 3H2O(g)
The products of combustion act as a stepping stone which enables a link with
carbon and hydrogen (the reactants) with propane (the product)
Route 2a involves the combustion of both carbon and hydrogen
3C (s) + 3O2 (g) 3CO2 (g) and 3H2 (s) + 1.5 O2 (g) 3H2O (g)
Route 2b involves the reverse combustion of propane
3CO2 (g) + 3H2O(l) 3C2H6 (g) + 41/2O2 (g)

DH1
3C (s) + 3H2 (g)

Route 1

Route DH 2a

C3H6 (g)
Route DH 2b

3CO2 (g) + 3H2O(g)

DH 1

= DH 2a + DH 2b

Route 2a DH c C= -394 kJ mol 1

DH c H = -286 kJ mol 1

-(3 x 286) = -858 kJ mol -1

DH 2a= -( 3x 394) = -1182 kJ mol -1 +
DH 2a = -2040 kJ mol 1
Route 2b DH c Propane = -2056 kJ mol 1
DH 2b = + 2058.5 kJ mol 1 (note the reverse sign)
-1
DH 1 = -2040 kJ mol -1 + (+ 2058.5 kJ mol 1) = 18.5 kJ mol

Summary:
enthalpy is a state function
and is path independent.

26

Industrial Chemistry
The UK chemical industry is the nations 4th largest manufacturing
industry and the 5th largest in the world.
The 3 largest sections are
(a) food, drink and tobacco,
(b) mechanical engineering and
(c) paper, printing and publishing
All chemical plants require a source of raw materials, which can
either be non-living eg minerals, or living, eg plants and
micro-organisms. (collectively known as biomass).
A chemical plant produces the desired products. The process used
to manufacture the product may be operated in continuous or
batch sequences.

Batch
For

OK for up to 100
tonnes per annum
Versatile
Good for multistep reactions

Against Contamination

At times, no
product is made.
Safety

Continuous
OK for over 1000
tonnes per annum
Good for fast
single step
processes
Easy to automate
Capital cost
Less flexible
Need to run at full
capacity

Fertiliser Industry
Haber process
Ammonia is manufactured from N2 and H2. The nitrogen is available from the
raw material, air. (something which is available naturally).
The hydrogen, like nitrogen, a feedstock for the manufacture of NH3.
Hydrogen is usually produced from methane.
Natural
gas

CH4 (g)

AIR

alkali

H2O(g)
Water

Catalyst
heat

Stage 1

Catalyst

Stage 2

Catalyst

Stage 3

N2(g) +
H2 (g)
CO2 removed

Haber Process
Stage 1 CH4 (g) + H2O (g) CO (g) + 3H2 (g) H = +210 kJ
1
Stage 2 4N2 (g) + O2 (g) + 2H2(g) 2H2O (g) + 4N2 (g)
H2 = -484 kJ
Stage 3 CO (g) + H2O (g) CO2 (g) + H2 (g)

H3 = -41 kJ

In order to achieve a ratio of 3x hydrogen to nitrogen, stage 1 and 3 need to be

3.5x greater than stage 2.

Combining the three stages

3.5 CH4 (g) + 4N2 (g) + O2(g) + 5H2O (g) 4N2 (g) +
12H2 (g) + 3.5 CO2
H1 = (+210 x 3.5) kJ H2 = -(484) kJ
(H1 + H2 + H3 ) Htotal = -41 kJ

H3 = -(41 x 3.5) kJ

Haber process
Reaction Conditions

N2 (g) + 3H2 (g)

Hf = -92 kJ

2NH3 (g)

Low temperature shifts the equilibrium to the right, but means

a slow reaction rate. Fe catalyst improves this.
A high pressure favours also shifts the equilibrium to the right because
this is the side with fewer gas molecules.
Temperatures around 500oC and pressures of over 150 atmospheres
give a yield of ammonia of about 15%.
Product removal: In practice, equilibrium is not reached as
unreacted gases are recycled and the ammonia gas is liquefied.

Sulphuric Acid Industry

Sulphuric acid is manufactured by the Contact Process.
Waste gases
Sulphur

O2(g)
Air

SO2(g)
burner

heat

feedstock

Stage 1

Stage 2

98% ac

Stage 3

Catalytic
SO3(g)
absorber
Converter
Cat=V2O5

water
mixer

H2SO

Petrochemical Industry
Grangemouth is one of the UKs major oil refineries and petrochemical
plants. The crude oil is processed to increase its market value.
Oil refining is a continuous process. The crude oil is processed to
increase its market value. The fractions produced have many uses
and heavier fractions are further processed by processes such as
cracking which produces key feedstock for the plastic industry.
Refinery gas, eg propane and butane bottled gas
Petrol, which is further purified and blended
Naphtha, feedstock for the plastic industry
Kerosine, aviation fuel
Diesel,
Fuel oil, eg ships, oil-fired power stations, industrial heating

residue, lubricating oil, waxes, bitumen

Natural gas
The market value of Natural Gas is increased by desulphurisation
and separating it into its constituent parts. Natural gas becomes a
liquid at below -161oC. Fractional distillation is then used to
separate out the constituents of natural gases in a continuous
process.

Natural
gases

methane
ethane
propane
butane
sulphur

Gas grid
Cracker (e
LPG

petrol

Pharmaceutical Industry
Drugs alter the biochemical processes in our bodies, for example,
changing the way we feel and behave. Drugs which lead to an
improvement in health are called medicines.
Once a new drug is discovered, it will be patented, the licence lasting
20 years. Many years of trials may be needed before the drug even
becomes commercially available. The Government is also involved in
this process, providing the necessary licensing for the new drug.
The Chemical Industry earns 1000 million pounds a year in invisible
earning for licensing fees for patented chemicals and processes.
Once the necessary licensing has been granted a pilot plant will be
built for small scale production to allow for product evaluation.
Full scale production is then implemented, where safety, environmental
and energy saving factors have to be considered.

Economic aspects
Energy in or out
products

Feedstock
REACTION
Separation
Co-products
preparation
Temp, pressure, catalyst
Recycle loop

Consideration has to be given to

Operating conditions
Costs, capital, fixed and variable
Use of energy
Location of the Chemical industry
Safety and the environment

Choices to be made
1. Cost, availability of feedstocks
2.Yield of the reaction
3. Can un-reacted materials be recycled
4. Can by-products be sold
5. Cost of waste disposal
6. Energy consumption, generating your own, conservation,
use of catalysts, recycling, (heat exchangers),
7. Environmental issues
Value added, eg the value of the products from crude oil

Crude
oil

naphtha

propene

1xs per tonne

3xs per tonne

s per tonne

polypropene
8xs per tonne

carpeting

20xs per tonne