CHEMICAL ENERGETICS

Unit 6

1
Types of Energy Calorimetry and Internal energy The First Law of Heat Capacity and
sign conventions Thermodynamics Enthalpy changes

Applications of
Hess’ Law in
calculating enthalpy
changes

2
Thermochemistry is
the study of the heat
changes that take place
during chemical
reactions.

Thermodynamics is the
study of the
interconversion of heat
and other forms of
energy.

3
A thermodynamic system Everything outside the The system is separated
is the region of the system is called the from the surroundings by
universe that we select surroundings. its boundary.
for investigation
Gas in a cylinder may constitute a
system.
Reaction vessel, e.g., titration flask

4
 System: open, closed and isolated
 UNIVERSE

Surroundings: every where else in universe

 Open system: can exchange matter and energy with surroundings

 Closed system: exchange energy only with surroundings.

 Isolated system: No exchange of anything with surroundings.

 7
© 2008 W. W. Norton & Company Inc. All rights reserved.
 When energy is
absorbed by a system
it is called an
ENDOTHERMIC
process (container
feels cold).

When energy is
released by a system
it is called an
EXOTHERMIC
process (container
feels hot).
8
 Energy – the capacity to do work (to move an object against an
opposing force) or to supply heat

 Joule – the SI unit of energy

 1 J = 1 kg m2 s-2

 Kinetic Energy, EK – energy an object has when it is moving

 Potential Energy, EP – “stored energy”, the energy an object has

because it is either attracted to or repelled by some other object.

9
ENERGY
 Law of Conservation of Energy states that:
“Energy cannot be created or destroyed but can be converted
from one form into another.”

 There are two main categories of energy: Potential Energy, EP,

and Kinetic Energy, EK, and it is possible to convert from one
form to the next.

 Potential: due to position or composition - can be converted to

work
PE = m x g x h
(m = mass, g = force of gravity, and h = vertical distance)

 Kinetic: due to motion of the object, KE = 1 mv 2

2
(m = mass, v = velocity)

10
For example:
 Thermal Energy: This is due to the kinetic energy of atoms and
molecules that are in motion.
 Can be measured by finding the temperature.

 Chemical Energy: This is due to potential energy stored in

bonds linking atoms together.
 Some of this energy is released when molecules react to form
more stable substances.

11
 The total internal energy of an isolated system is
constant.

 The total internal energy “E” or “U” of the system is the

sum of all the kinetic energy and potential energy for
all the molecules or ions in the system.

 It is a state function.

 Internal energy cannot be determined directly.

12
 It is important, however, that we are able to
measure accurately the energy that enters
or leave the system.

 The total internal energy (U) = Ek + Ep for

all molecules or ions in the system.

 Therefore the change in internal energy

DU = Ufin – Uinit or DE = Efin – Einit

13
 DE = Efin – Einit
 By convention:
 Loss of energy (from system) is negative Ef < Ei
 Gain of energy (into system) is positive Ef > Ei

 Energy changes are measured from the point of view of the system

14
 Work is the force that
produces the movement
of an object times the
distance moved.

WORK Work = Force × distance

w=F×d

15
C3H8 (g) +5 O2 (g) 3CO2 (g) + 4H2O (g) 16
 Work is the force that
produces the
Work = Force ×
movement of an
distance
object times the
distance moved.

w=F×d F = -Pressure × Area

WORK
F = -P x A w = -P x A× d

ΔV = A× d w = -PΔV

17
C3H8 (g) + 5O2 (g)→ 4H2O(g) + 3CO2(g)
 ninitial = 6 moles of gas
 nfinal = 7 moles of gas
 Dn = 7-6 = 1
 Since Dn is proportional to DV; DV
is +ve and the overall energy
(work) is negative since w = -pDV
 So work is done by the system
against the external pressure
 For an ideal gas p│DV│= nRT
3H2(g) + N2(g) → 2NH3(g)
ninitial = 4 moles of gas
nfinal = 2 moles of gas
Dn = 2-4 = -2
• Since Dn is proportional to DV; DV is –ve
and the overall energy (work) is positive
since w = -pDV.
• So work is done on the system by the
external pressure.
• If there is no change in volume, then
no work is done.
CH4(g) + 2CO2(g) → CO2(g) + 2H2O(g)
 A system can exchange energy with its surroundings by heat transfer or
by doing work.
 Thus the change in the internal energy DU = heat change + P-V work
 DU = q + w Another way of writing the 1 st law of thermodynamics

 i.e. DU = q – PDV

 Thus q = DU + PDV

 Note q is +ve when the system gains heat and –ve when the system loses
heat
  What is the change in the internal
energy, ∆U, of a system that
releases 2,500 J of heat and that
does 7,655 J of work on the
surroundings at constant pressure?

DU = q + w
ACTIVITY q = -2500 J
w = -7655
DU = (-2500) + (-7655)
DU = -10, 155 J

20
 Recall: q = DU + PDV

 At constant volume:
 qv = DU since DV = 0

 At constant pressure:
 qp = DH = DU + PDV

 DH is a special symbol for q at constant pressure, P, and is called the

heat of reaction or enthalpy change of the reaction.
 The enthalpy H = U + PV is defined as such.
 It is the enthalpy change DH that is important in reacting systems.
 DH is a state function and like any thermodynamic parameter:
 DH = ∑Hproducts - ∑Hreactants or DH = Hf – Hi

 Under laboratory conditions and in cases where gases are not involved
DH ≈ DU and PV work is small.

 When DH is +ve, the process is said to be endothermic (i.e. the system

absorbs heat).
 When DH is –ve, the process is said to exothermic (i.e. the system
emits/release heat).

 Note also DH is a state function it means that the reverse of an

endothermic process is exothermic and vice versa.
• Most reactions, including
combustion and
neutralisations are
exothermic.

• They result in transfer of

heat from the system to the
surrounding.

• As heat is given out, the

products of exothermic
reactions have less energy
than the reactants.

23
 EXOTHERMIC REACTIONS

For an exothermic
reaction the heat content
of the system decreases.

Therefore the enthalpy

change (∆H) is –VE.

The combustion of methane

CH4(g) + 2O2(g)  CO2(g) + 2H2O(l); DH = -890.4 kJ

24
 ENDOTHERMIC REACTIONS
 For an endothermic reaction the heat
content of the system increases.

 Therefore the enthalpy change (∆H) is

+VE.

 Endothermic reactions are those in

which heat is transferred from the
surroundings to the system. i.e. heat
energy is absorbed by the system.

 Consequently the products of the

reaction have more energy that the
reactants.

Photosynthesis
6CO2(g) + 6H2O(l)  C6H12O6 (g) + 6O2(g) ; DH = +2802.5 kJ 25
26
 A temperature of 298
K or 25°C

A pressure of 101 kPa

STANDARD or 1 atm
CONDITIONS
FOR ENTHALPY
CHANGES Concentrations of 1.0
M for all solutions

All the substances in

their standard states.

27
 The temperature, pressure and physical state of reactants and
products must be specified.

 Under different conditions, and if the product, for example, is

liquid or gaseous, the enthalpy of the reaction is normally
different.

 E.g.

CH4(g) + 2O2(g)  CO2(g) + 2H2O(l) DHorxn = -890.4 kJ

CH4(g) + 2O2(g)  CO2(g) + 2H2O(g) DHorxn = -714.4 kJ

28
 The heat released or absorbed in a particular reaction
depends on the particular amount of reactants:

N2 (g) + 3 H2 (g)  2 NH3 (g) DHrxno = -92.2 kJmol-1

For 0.2 moles of N2 gas in excess H2, the relevant enthalpy

change, DH = 0.2  -92.2 kJ = -18.4 kJ

29
 How do we measure the enthalpy of a reaction?
 The heat transferred during a reaction can be determined by carrying it
out in a calorimeter.

 As the reaction proceeds, the temperature is observed and used to calculate the
heat change (at constant pressure).
 The heat change of substance or system is directly proportional to the
temperature change DT.
 q a DT
 q = CDT
 Here C is the amount of heat required to raise the temperature of the
substance or system by 1 K and is called the heat capacity.
 DT is the temperature change for the process (DT = Tfin – Tinit).

 The heat capacity varies with the amount or capacity of the system.
 Specific heat capacity is the amount of heat necessary to raise the
temperature of 1g of substance by 1 K.
 q = mCDT
 C = 4.18 Jg-1K-1 for water.

 Alternatively one can use the molar heat capacity c m = c /(# of moles)
 q = cmnDT where n = # of moles
 What is the specific heat capacity of silicon if it takes 192 J to
raise the temperature of 45.0 g of Si by 6.0 0C?
 q = mCDT

 C = q/mDT
 C = 192 J/ (45.0 g x 6.00C)
 C = 0.71 J/g 0C

32
 For combustible
substances, the heat of
combustion can be
calculated from
measuring temperature
changes in water that the
burning substance is
used to heat.

33
 When the heat from an exothermic reaction is
absorbed by the water, the temperature of the
water increases.

CALCULATION The heat produced by the combustion reaction

can be calculated if it is assumed that all the
OF ENTHALPY heat is absorbed by the water.

CHANGES- HEAT Heat change (q) = -(heat

OF COMBUSTION change of water)

q= -(mwater  Cwater 
∆T)

34
 Calculate the enthalpy of combustion of ethanol in kJ/mol, if
0.45 g ethanol was used to heat 200 g of water. The temperature
increase in the water was 13.00 K. The specific heat capacity of
water is 4.18 Jg-1K-1.
Heat change (q) = - (mwater  Cwater  ∆T)

Enthalpy of combustion = q

No. of moles of fuel

35
q  Mass water  C water  ΔTwater 
q  (200g  4.18Jg 1K 1 13.00K
q  - 10,868 J
- ve sign shows that heat was evolved, i.e. an exothermic reaction

0.45
moles of ethanol  - 10,868 J
46.08
- 10,868 J
1 mole ethanol  1mole  1112883.2 J
9.8 10 moles
-3

 1.1103 kJ/mol
Ans : enthalpy of combustion of ethanol   1.1103 kJ/mol

36
q (comb.) = -[q (water) + q (calorimeter)]
q (comb.) = -[mCDT + CDT ]
 The enthalpy changes of reactions in
solution can be calculated by carrying
out the experiment in an insulated
container, like a Styrofoam cup.

 In these reactions, the molar enthalpy

of reaction is dependent on the
limiting reagent.

38
 Consider the following reaction:

KOH (aq) + HCl (aq) → KCl (aq) + H2O (l)

The data below are for an experiment to determine the enthalpy
change of this reaction.
50.0 cm3 of a 0.500 M solution of KOH was mixed with 50.0 cm 3 of a
0.500 M solution of HCl in a Styrofoam container.
Initial temperature was = 19.6°C
Final temperature was = 23.1°C
Calculate the enthalpy change in kJ/mol. Assume the specific heat
capacity of the solution is the same as that of water and that the density
of the solution is 1g/cm 3.

 Heat change (q) = - (msolution  C  ∆T)

 Enthalpy of neutralization = q / no. of moles of water formed

39
 Special terms are assigned to enthalpy changes for particular
types of chemical reactions and physical processes.

 Such processes include:

 Formation
 Bond dissociation
 Solution
 Combustion
 Neutralization
 Melting
 Sublimation, etc.

40
 The enthalpy change of bond dissociation (or bond dissociation
enthalpy) DH diss: the energy required to break 1 mole of
molecule of a particular type of bond, X2:

X-X  2X

The enthalpy change of combustion (enthalpy of combustion)

DHcomb: The energy released by 1 mole of a substance is
completely burned in air or O2 under standard conditions.

 The enthalpy change of formation, DHf: the energy change when

1 mole of a compound is formed from its elements in their

standard states.

41
The enthalpy change of neutralisation (enthalpy of neutralisation)

DHneut: The energy evolved when 1 mole of an acid or base is

completely neutralized. For all strong acids or bases, its value is
approximately -57.5 kJ.

The enthalpy change of sublimation DHsub : The energy required

to convert 1 mole of a solid substance into the gaseous phase at

the same temperature.

42
 Hess’ Law
 HESS’ LAW: The overall enthalpy change for a reaction is equal to the
sum of the enthalpy changes for the individual steps in the reaction.

 This is a manifestation of a property of state functions: All routes that

lead from a common origin to a particular destination give the same
value for a state function.

 Example:
Step 1: A + D  E DH1
Step 2: 2B + D  2F DH2
Step 3: E + 2F  C + 2D DH3
A + 2B C DHrxn = DH1+ DH2 + DH3

43
 Calculating Enthalpy Changes:
Using Enthalpy Changes of Intermediate Stages
 The Haber process is a reaction with the overall result of producing NH3 (g)
from N2 (g) and H2 (g) according to the chemical equation:
N2 (g) + 3H2 (g)  2NH3 (g)
The reaction however proceeds through steps:
Step 1: N2 (g) + 2 H2 (g)  2 N2H4 (g)
DHo1 = +95.4 kJ
Step 2: 2 N2H4 (g) + H2 (g)  2 NH3 (g)
DHo2 = -187.6 kJ

N2 (g) + 3 H2 (g) + 2 N2H4 (g)  2 N2H4 (g) + 2 NH3 (g) DHrxn = DH1 + DH2

Overall: N2 (g) + 3 H2 (g)  2 NH3 (g) DHorxn = -92.2 kJ

 These steps add up to give the overall reaction above

44
 Calculate the standard enthalpy change (∆H) for the reaction:

C (s) + ½ O2(g) → CO(g)

From the information given below:

C(s) + O2 (g) → CO2 (g) ∆H= -394 kJmol-1
CO(g) + ½O2 (g) → CO2 (g) ∆H= -283 kJmol-1

45
 Using the equations below:

C(s) + O2 (g) → CO2 (g) ∆H = -390 kJ

Mn (s) + O2 (g) → MnO2 (s) ∆H = -520 kJ

What is ∆H (in kJ) for the following reaction?

MnO2 (s)+ C(s) → Mn (s) + CO2 (g) ∆H =?

46
 Calculate ∆H for the reaction
4 NH3 (g) + 5 O2 (g) → 4 NO (g) + 6 H2O (g)
from the following data:
 N2 (g) + O2 (g) → 2 NO (g) ∆H = -180.5 kJ
 N2 (g) + 3 H2 (g) → 2 NH3 (g) ∆H = -91.8 kJ
 2 H2 (g) + O2 (g) → 2 H2O (g) ∆H = -483.6 kJ

47
Solution
[N2 (g) + O2 (g) → 2 NO (g) DH = -180.5 kJ] × 2
[2 NH3 (g) → N2 (g) + 3 H2 (g) DH = +91.8 kJ] × 2
[2 H2 (g) + O2 (g) → 2 H2O (g) DH = -483.6 kJ] × 3

2N2 (g) + 2O2 (g) → 4 NO (g) DH = -361 kJ

4 NH3 (g) → 2N2 (g) + 6 H2 (g) DH = +183.6 kJ
6 H2 (g) + 3O2 (g) → 6 H2O (g) DH = -1450.8 kJ

Overall: 4 NH3 (g) + 5 O2 (g) → 4 NO (g) + 6 H2O (g)

DH = (-361 + 183.6 + (–1450.8)) kJ = –1628.2 kJ

 Enthalpy change of formation (DHof): the formation of 1 mole
of a substance in its standard state from its constituent
elements in their standard (or reference) states.
 The reaction to form a substance from its elements can be, and
often is, hypothetical.

 DHorxn = ∑[∆Hf products] – ∑[∆Hf reactants]

 By definition, the most stable form of any element in its

standard state has DHof = 0.

49
 Consider rxn: CO (g) + 1/2 O2(g)  CO2(g). Calculate DHorxn.

DHof (CO) = -110 kJ mol-1

DHof (CO2) = -393.5 kJ mol-1

DHof (O2) = 0 kJ mol-1

Thus, in accordance with the general formula:

DHorxn = ∑[∆Hf products] – ∑[∆Hf reactants]

DHorxn = DHof (CO2) – [DHof (CO) + DHof (O2)]

DHorxn = DHof (CO2) - DHof (CO)

= -393.5 kJ mol-1 – (-110 kJ mol-1)

50
= -283.5 kJ mol-1
• Consider the reaction for the fermentation of glucose:
C6H12O6 (s)  2 C2H5OH (l) + 2 CO2 (g). Calculate DHorxn.

DHorxn = [2DHof (C2H5OH) + 2DHof (CO2)] - [DHof (C6H12O6)]

DHorxn = 2 (-277.7) + 2(-393.5) -1(-1260)
DHorxn = -82 kJ

• Therefore, the reaction is exothermic by 82 kJ.

• Consider the reaction:

2 C2H2(g) + 5 O2(g)  4 CO2(g) + 2 H2O(g). Calculate DHorxn.

DHorxn = [4DHof (CO2) + 2DHof (H2O)] - [2DHof (C2H2) + 5DHof (O2) ]

DHorxn = 4 (- 393.5) + 2(-241.8) -2(226.7)
DHorxn = -2511.0 kJ.
51
 Activity

Calculate DHof for C6H6 (l) (in kJ mol-1) given the following
information:
2 C6H6 (l) + 15 O2 (g)  12 CO2 (g) + 6 H2O (l)
DHocomb = -6534 kJ mol-1
DHof (CO2) = -393.5 kJ mol-1
DHof (H2O) = -285.8 kJ mol-1

 DHocomb = [12DHof (CO2) + 6DHof (H2O)] - [2DHof (C6H6) + 15DHof (O2) ]

 -6534 = 12 (-393.5) + 6(-285.8) - 2DHof (C6H6)

 -6534 = -4722 – 1714.8 - 2DHof (C6H6)
 6534 = - 6436.8 - 2DHof (C6H6)
 2DHof (C6H6) = 97.2

Answer: DHof (C6H6 ) = 48.6 kJ mol-1

52
 CALCULATING ENTHALPY CHANGES: USING BOND DISSOCIATION
ENERGIES

 Despite the usefulness of using DHf to determine enthalpy changes for

reactions, DHf values have not been found for all the millions of known
chemicals compounds.

 Where DHf values are not available it is possible to get approximate values

for enthalpy changes by using average bond dissociation energies (DHdiss or

B.D.E.).

Generally: X—X  2 X DHodiss

 For Example: Cl—Cl  2Cl DHodiss = 243 kJ mol-1

 Bond dissociation energies are always positive as energy must always be

put into a bond to break it.

53
 By similar application of Hess’ Law, it is possible to calculate an
approximate enthalpy change for any reaction by subtracting the total
energy of bonds formed in the products from the total energy of bonds
broken in the reactants.

For the reaction: H—H (g) + Cl—Cl (g)  2H—Cl (g)

DHorxn = ∑BDE(bonds broken) - ∑BDE(bonds formed)
DHorxn = ∑BDE(reactant bonds) - ∑BDE(product bonds)

Bonds broken: H2 (g) and Cl2 (g);

Bonds formed: HCl (g)
 DHorxn = [B.D.E.HH + B.D.E.ClCl ]- 2(B.D.E.HCl )
= [1 × 243 kJ + 1 × 436 kJ ]- [2 × 432 kJ]
= -185 kJ
54
 Consider the reaction:
CH4 + 3Cl2  CHCl3 + 3HCl DHorxn = -327 kJ mol-1;
B.D.E.(CH) = 410 kJ mol-1 ;
B.D.E.( ClCl = 243 kJ mol-1;
B.D.E.( CCl = 330 kJ mol-1.

What is the value of B.D.E.HCl ?

DHorxn = [4(B.D.E.CH )+ 3(B.D.E.ClCl )]– [B.D.E.CH + 3(B.D.E.CCl )+
3(B.D.E.HCl)]
-327 = [4(410) +3(243)] – [(410) +3(330)] + 3(B.D.E.HCl)]
-327 =[1640 + 729] – [410 + 990 + 3(B.D.E.HCl)]
-327 = 2369 – 1400 - 3(B.D.E.HCl)]
3(B.D.E.HCl)] = 1296/3

B.D.E.HCl = 432 kJ mol -1;

55
 Activity

For the reaction: 2NH3 (g) + Cl2 (g)  N2H4 (g) + 2HCl (g).

Calculate DHorxn.

DHorxn = ∑(bonds broken) - ∑(bonds formed)

DHorxn = [6(B.D.E.NH )+ B.D.E.ClCl ]– [4(B.D.E.NH )+ B.D.E.NN + 2(B.D.E.HCl)]

DHorxn = [6(390kJ) + 243kJ] – [4(390kJ) + 240kJ + 2(432kJ)]

=  81 kJ

56
 THE BORN-HABER CYCLE

• The enthalpy of formation of a solid compound can

be analyzed as being due to several contributions.

• The combination of these contributions form a

thermochemical cycle known as the Born-Haber
Cycle.

• For example:
• Construct a Born Haber cycle for NaCl.
Na (s) + ½ Cl2 (g)  NaCl (s)

57
 Ionization energy (Ei) is the amount of energy required to remove the highest energy electron
from an isolated neutral atom in the gaseous state.

 Na(g)  Na+(g) + e - Ei = +495.8 kJ/mol

 Electron Affinity (Ea) is in the energy change that occurs when an electron is added to an
isolated atom in the gaseous state.

 Cl(g) + e -  Cl-(g) Ea = -348.6 kJ/mol

 Lattice energy is the amount of energy that must be supplied to break up an ionic solid into its
gaseous ions.

 NaCl(s)  Na+(g) + Cl-(g) +787 kJmol-1

 Na+(g) + Cl-(g)  NaCl(s) -787 kJmol-1

58
 BORN-HABER CYCLE for NaCl
Na+(g) + Cl (g)

122 kJ/mol Electron Affinity

2 Cl2 (g)  Cl(g)
Bond Dissociation: 1/

Cl(g) + e -  Cl-(g)
-348.6 kJ/mol
Na+(g) + 1/
2 Cl2 (g)
Na+(g) + Cl- (g)
1st Ionization: Na(g)  Na+(g) + e- 495.8 kJ/mol
-Lattice Energy = -787 kJmol-1
Na(g) + 1/2 Cl2 (g)
Na+(g) + Cl-(g)  NaCl(s)
Sublimation: Na(s)  Na(g) 107.3 kJ/mol

Na(s) + 1/2 Cl2 (g)

Na(s) + 1/2Cl2(g)  NaCl(s)
∆HFormation -411 kJ mol-1

NaCl (s)

∆Hf = ∆Hsub.Na + ∆HI.ENa + (∆HB.D.E Cl2) + ∆HE.A. Cl - ∆HL.E. NaCl 59

 Construct the Born Haber cycle to show the
formation of Magnesium chloride.

60
 BORN-HABER CYCLE for MgCl2
Mg2+(g) + 2Cl (g)

Bond Dissociation: 122 kJ/mol Electron Affinity

2nd Ionization: 1450.7 kJ/mol -348.6 kJ/mol

1st Ionization 737.7 kJ/mol

Lattice Energy
147.7 kJ/mol
Sublimation: Mg2+(g) + 2Cl-(g)  MgCl2(s)

Mg(s) + Cl2(g)  MgCl2(s)

∆H Formation -642kJ/mol

MgCl2 (s)

∆H formation =∑(all the individual enthalpy changes) 61

 BORN-HABER CYCLE for MgCl2
Mg2+(g) + 2Cl (g)

Bond Dissociation: Cl2(g)  2Cl(g) 243 kJ/mol Electron Affinity

2Cl(g) + 2e -  2Cl-(g)
Mg2+(g) + Cl2 (g)
2nd Ionization: Mg+(g)  Mg2+(g) + e - 1450.7 kJ/mol -697.2 kJ/mol

Mg+(g) + Cl2 (g) Mg2+(g) + 2Cl- (g)

1st Ionization Mg(g)  Mg+(g) + e - 737.7 kJ/mol

Mg(g) + Cl2 (g) -Lattice Energy -2524 kJ/mol

Sublimation: Mg(s)  Mg(g) 147.7 kJ/mol
Mg2+(g) + 2Cl-(g)  MgCl2(s)

Mg(s) + Cl2 (g)

Mg(s) + Cl2(g)  MgCl2(s)
∆H Formation -642kJ/mol

MgCl2 (s)

∆H formation =∑(all the individual enthalpy changes) 62