9.

0 THERMOCHEMISTRY

Thermochemistry


A study of heat change in chemical reactions.

Concept of Enthalpy

Enthalpy, H


The heat content of a system or total energy in the system Enthalpy, H of a system cannot be measured when there is a change in the system. Example: system undergoes combustion or ionisation.

Enthalpy change, H


equals the heat gained or lost at constant pressure H.

Thermochemistry
 

A study of heat change in chemical reactions. Two types of chemical reactions:

 

Exothermic Endothermic

Exothermic reactions
y

Enthalpy of products < Enthalpy of reactants, H is negative. Energy is released from the system to the surroundings.

Consider the following reaction: A (g) + B (g) C (g) (reactants) (product)

H = ve

reactants enthalpy H= -ve products reaction pathway

Energy profile diagram for exothermic reaction

Endothermic Reactions


Enthalpy of products > enthalpy of reactants, positive

H is

Energy is absorbed by the system from the surrounding

Consider the following reaction A (g) + B (g) C(g) (reactants) (product)

H = + ve

Energy profile of diagram endothermic reactions

Enthalpy of Reaction, H and Standard Condition



Enthalpy of reaction:  The enthalpy change associated with a chemical reaction. Standard enthalpy, H  The enthalpy change for a particular reaction that occurs at 298K and 1 atm (standard state)

Thermochemical Equation


The thermochemical equation shows the enthalpy changes. Example : H2O(s) H2O(l) H = +6.01 kJ

1 mole of H2O(l) is formed from 1 mole of H2O(s) at 0C, H = +6.01 kJ However, when 1 mole of H2O(s) is formed from 1 mole of H2O(l), the magnitude of H remains the same with the opposite sign of it. H2O(l) H2O(s) H = 6.01 kJ

Types of Enthalpies


There are many kind of enthalpies such as:  Enthalpy of formation  Enthalpy of combustion  Enthalpy of atomisation  Enthalpy neutralisation  Enthalpy hydration  Enthalpy solution

Enthalpy of Formation, Hf


The change of heat when 1 mole of a compound is formed from its elements at their standard states.
H2 (g) + O2(g) H2O (l)

Hf = 286 kJ mol1

The standard enthalpy of formation of any element in its most stable state form is ZERO. H (O2 ) = 0 H (Cl2) = 0

Enthalpy of Combustion, Hc


The heat released when 1 mole of substance is burned completely in excess oxygen.
CO2(g)

C(s) + O2(g)

Hc = 393 kJ mol1

Enthalpy of Atomisation, (Ha



The heat change when 1 mole of gaseous atoms is formed from its element (Ha is always positive because it involves only breaking of bonds e.g: Na(s) p Na(g) Cl2(g) p Cl(g) (Ha = +109 kJ mol-1 (Ha = +123 kJ mol-1

 

Enthalpy of Neutralization, Hn


The heat change when 1 mole of water, H2O is formed from the neutralization of acid and base . HCl(aq)+ NaOH(aq) NaCl(aq) +H2O(aq) Hn = 58 kJ mol1

Enthalpy of Hydration, (Hhyd

 

The heat change when 1 mole of gaseous ions is hydrated in water. e.g: Na+(g) p Na+(aq) (Hhyd = 406 kJ mol-1 Cl-(g) p Cl-(aq) (Hhyd = 363 kJ mol-1

Enthalpy of Solution, (Hsoln

The heat change when 1 mole of a substance is dissolves in water.  e.g: KCl(s) p K+(aq) + Cl(aq) (Hsoln = +690 kJ mol-1

Enthalpy of Sublimation, (Hsubl

The heat change when one mole of a substance sublimes (solid into gas).
(H r subl

I2 (s)

I2(g)

(Hsubl =

+106 kJ mol1

Calorimetry
  

A method used in the laboratory to measure the heat change of a reaction. Apparatus used is known as the calorimeter Examples of calorimeter
 

Simple calorimeter Bomb calorimeter

Simple calorimeter


The outer Styrofoam cup insulate the reaction mixture from the surroundings (it is assumed that no heat is lost to the surroundings) Heat release by the reaction is absorbed by solution and the calorimeter

A bomb calorimeter

Important Terms in Calorimeter



Specific heat capacity, c  Specific heat capacity, c of a substance is the amount of heat required to raise the temperature of one gram of the substance by one degree Celsius (Jg 1rC1). Heat capacity, C  Heat capacity,C is the amount of heat required to raise the temperature of a given quantity of the substance by one degree Celsius (JrC1)

Heat released by substance

Heat absorbed by calorimeter

q = mcT
q = heat released by substance m= mass of substance C= specific heat capacity T = temperature change

Basic Principle in Calorimeter

Heat released by a reaction = Heat absorbed by surroundings

Surroundings may refer to the: i. Calorimeter itself or; ii. The water and calorimeter qreaction= mc T or C T

Example 1 In an experiment, 0.100 g of H2 and excess of O2 were compressed into a 1.00 L bomb and placed into a calorimeter with heat capacity of 9.08 x 104 J0C1. The initial temperature of the calorimeter was 25.0000C and finally it increased to 25.155 0C. Calculate the amount of heat released in the reaction to form H2O, expressed in kJ per mole.

Solution Heat released = Heat absorbed by the calorimeter q = CT = (9.08 X 104 J0C-1) X (0.1550C) = 1.41 X 104 J = 14.1 kJ H2(g) + O2(g) mole of H2 = 0.100 2.016 = 0.0496 mol H2O(c)

moles of H2O

mole of H2

0.0496 mol of H2O released 14.1 kJ energy 1 mol H2O released

14.1 = 0.0496

kJ

Heat of reaction, H

= 284 kJ = - 284 kJ mol1

Example 2 1. Calculate the amount of heat released in a reaction in an aluminum calorimeter with a mass of 3087.0 g and contains 1700.0 mL of water. The initial temperature of the calorimeter is 25.0C and it increased to 27.8C.

Given: Specific heat capacity of aluminum = 0.553Jg-1 C-1 Specific heat capacity of water = 4.18 Jg-1 C-1 Water density = 1.0 g mL-1 T = (27.8 -25.0 )C = 2.8C Solution
Heat released = Heat absorbed by aluminium calorimeter + Heat absorbed by water

q = mwcw T + mccc T = (1700.0 g)(4.18 Jg-1 C-1)(2.8 C) + (3087.0 g)(0.553 Jg-1 C-1)(2.8C) = 24676.71 J = 24.7 kJ

HESSS LAW

Hess Law


Hesss Law states that when reactants are converted to products, the change in enthalpy is the same whether the reaction takes place in one step or in the series of steps. The enthalpy change depends only on the nature of the reactants and products and is independent of the route taken.
A
(H r 2
r (H1

r (H 3

r (H1 ! (Hr  (Hr 2 3

Algebraic Method
Step 1
i. List all the thermochemical equations involved
i.C O p CO (S) 2( g ) 2( g ) (H ! - 393kJmol- 1 (H ! -286kJmol- 1 (H ! -1560kJmol
-1

ii .H

1 O pH O 2 2( g ) 2( g ) 2 ( g) iii.C H 7 O p 2CO  3H O 2 2( g ) 2 6( g ) 2( g ) 2 ( g)

Algebraic Method
Step 1
i. List all the thermochemical equations involved
i.C O p CO (S) 2( g ) 2( g ) (H ! - 393kJmol- 1 (H ! -286kJmol- 1 (H ! -1560kJmol
-1

ii .H

1 O pH O 2 2( g ) 2( g ) 2 ( g) iii.C H 7 O p 2CO  3H O 2 2( g ) 2 6( g ) 2( g ) 2 ( g)

ii. Write the enthalpy of formation reaction for C2H6

(H ! ? f C  3H p C H ( s) 2( g ) 2 6( g )

iii. Add the given reactions so that the result is the desired reaction.
(i ) v 2 (ii ) v 3 2C( S )  2O2( g ) p 2CO2( g ) 3 H 2( g )  3 O2( g ) p 3 H 2O( g ) 2 (H1 ! 2 v -393 kJ (H 2 ! 3 v -286kJ

reverse (iii) 2CO 2(g)  3 H 2O( g ) p C 2 H 6( g )  7 O2( g ) (H3 ! 1560kJ 2 _______________________________________________________________ (H f ! ? 2C ( s )  3 H 2( g ) p C 2 H 6( g ) - 84kJ (H f ! (H1  (H 2  (H3 ! -84kJ

Energy Cycle Method

Draw the energy cycle and apply Hesss Law to calculate the unknown value.

HO f 2C (s ) + 3H2 (g) H O = 3(-286) 2 HO 1 = 2(-393) 2CO2 (g) + 3H2O (g) 2O2 (g) 3/2 O2 (g) 7/2 O2 (g) HO = - (-1560) 3 C2 H6 (g)

 = 2( H ) + 3((H ) + Hf 1 2 ! -786 - 858  1560 -1 ! -84 kJmol

H3

Example 1 The thermochemical equation of combustion of carbon monoxide is shown as below. C(s) + O2(g) CO(g) =? r (H given : (H r kJ mol-1 C(s) + O2(g) CO2(g) H= -394 CO(s) + O2(g) CO2(g) H= H r kJ mol-1 ( -283 Calculate the enthalpy change of the combustion of carbon to carbon monoxide.

Example 2 Calculate the standard enthalpy of formation of methane if the enthalpy of combustion of carbon, hydrogen and methane are as follows: r H [C(s)] = -393 kJ mol-1 (H c = -293 kJ mol-1 r H [H2(s)] (H c = -753 kJ mol-1 r H [CH4(s)]
(H c

Example 3  Standard enthalpy of formation of ammonia, hydrogen chloride and ammonium chloride is -46.1 kJ mol-1, -92.3 kJ mol-1, 314.4 kJ mol-1 respectively. Write the thermochemical equation for the formation of each substance and calculate the enthalpy change for the following reaction. NH3(g) + HCl (g) NH4Cl(s)

Exercise 1.Calculate the enthalpy of formation of benzene if : H (CO2(g) ) = -393.3 kJ mol-1 H (H2O(l) ) = -285.5 kJ mol-1 r H (C6H6(l) ) = -3265.3 kJ mol-1 (H f
(H r f (H r f

Born-Haber Cycle

Lattice Energy, (Hlattice



is the energy required to completely separate one mole of a solid (ionic compound) into gaseous ions

e.g: NaCl(s) p Na+(g) + Cl-(g)

(Hlattice = +771 kJ mol-1 (lattice dissociation)

Na+(g) + Cl-(g) p NaCl(s)



(Hlattice = -771 kJ mol-1 (lattice formation) The magnitude of lattice energy increases as  the ionic charges increase  the ionic radii decrease

There is a strong attraction between small ions and highly charged ions so the (H is more negative. (H for MgO is more negative than (H for Na2O because Mg2+ is smaller in size and has bigger charge than Na+, therefore (Hlattice (MgO) > (Hlattice (Na2O)

Hydration Process of Ionic Solid



Na+ and Cl- ions in the solid crystal are separated from each other and converted to the gaseous state ((Hlattice) The electrostatic forces between gaseous ions and polar water molecules cause the ions to be surrounded by water molecules ((Hhydr)

(Hsoln = (Hlattice + (Hhdyr

Na+ and Cl- ion in the gaseous state

Heat of Solution
Na+ and Cl- ion in the solid state Hydrated Na+ and Cl- ion

Born-Haber Cycle
  

The process of ionic bond formation occurs in a few stages. At each stage the enthalpy changes are considered. The Born Haber cycle is often used to calculate the lattice energy of an ionic compound. In the Born-Haber cycle energy diagram, by convention, positive values are denoted as going upwards, negative values as going downwards. Consider the enthalpy changes in the formation of sodium chloride.

Example :
Na(s) 
 i. ii. iii. iv. v. vi.

1 2

Cl2(g) p NaCl(s)
= = = = = = -411 kJmol-1 +108 kJmol-1 +500 kJmol-1 +122 kJmol-1 -364 kJmol-1 ?

Given; Enthalpy of formation NaCl Enthalpy of sublimation of Na First ionization energy of Na Enthalpy of atomization of Cl Electron affinity of Cl Lattice energy of NaCl

Example: A Born-Haber cycle for NaCl

energy Na+(g) + e Ionisation Energy of Na Na(g) + Cl(g) + Cl(g) Electron Affinity of Cl Na+(g) + Cl- (g)

(HaCl
Na(g) + Cl2(g) +ve Lattice energy

(HaNa E=0
-ve Na(s) + Cl2(g)

From Hess s Law: (Hf

NaCl

(Hf NaCl
NaCl(s)

= (HaNa + (HaCl +IENa + EACl + Lattice Energy

Calculation:
(H0 ! (HS  IE  (Ha( Cl )  EA  (Hlattice f (Hlattice ! (H0  ? HS  IE  (Ha( Cl )  EAA ( f (Hlattice ! 411  ? 108kJ  500kJ  122kJ   364kJ A kJ (Hlattice ! 777kJ

Exercise:
 i. ii. iii. iv. v. vi.

Construct a Born-Haber cycle to explain why ionic compound NaCl2 cannot form under standard conditions. Use the data below: Enthalpy of sublimation of sodium = +108 kJmol-1 First ionization energy of sodium = +500 kJmol-1 Second ionization energy of sodium = +4562 kJmol-1 Enthalpy of atomization of chlorine = +121kJmol-1 Electron affinity of chlorine = -364 kJmol-1 Lattice energy of NaCl2 = -2489 kJmol-1