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Thermochemistry

Chapter 1 / Thermochemistry

Chapter one outline

1.1 The Nature of Energy and Types of Energy

1.2 Energy Changes in Chemical Reactions

1.3 Introduction to Thermodynamics

1.4 Enthalpy of Chemical Reactions

1.5 Calorimetry

1.6 Standard Enthalpy of Formation and Reaction

1.7 Heat of Solution and Dilution

2

Chapter 1 / Thermochemistry

1.1 The Nature of Energy and Types of Energy

• Kinetic energy is the energy produced by a moving object

• Radiant energy or solar energy comes from the sun and is earth’s primary energy

source

• Thermal energy is the energy associated with the random motion of atoms and

molecules

• Chemical energy is the energy stored within the bonds of chemical substances

• Nuclear energy is the energy stored within the collection of neutrons and protons in

the atom

• Potential energy is the energy available by virtue of an object’s position

3

Chapter 1 / Thermochemistry

1.2 Energy Changes in Chemical Reactions

the form of heat.

Heat is the transfer of thermal energy between two bodies that are at different

temperatures. (Heat always flows from a wormer object to a cooler object.)

4

Chapter 1 / Thermochemistry

1.2 Energy Changes in Chemical Reactions

900C

400C

greater thermal energy

The temperature of a substance is directly related to the energy of its

particles

Particles vibrating fast = hot

Particles vibrating slow = cold

Thermal energy is the total energy of all the particles that make up a

substance 5

Chapter 1 / Thermochemistry

1.2 Energy Changes in Chemical Reactions

The system is the specific part of the universe that is of interest in the study.

The surrounding are the rest of the universe outside the system

There are 3 types of systems:

6

Exchange: mass & energy energy nothing

Chapter 1 / Thermochemistry

1.2 Energy Changes in Chemical Reactions

Essentially all chemical reactions and changes in physical state involve either release of

heat or absorption of heat.

Exothermic process is any process that gives off heat – transfers thermal energy from

the system to the surroundings.

Endothermic process is any process in which heat has to be supplied to the system from

the surroundings.

7

Chapter 1 / Thermochemistry

1.2 Energy Changes in Chemical Reactions

Exothermic Endothermic

8

Chapter 1 / Thermochemistry

1.3 Introduction to Thermodynamics

energy from one form to another and the direction of reaction (relationship

between heat and other forms of energy).

State functions are properties that are determined by the state of the system, regardless

of how that condition was achieved.

Examples of the properties : energy, pressure, volume, temperature

DE = Efinal - Einitial

DP = Pfinal - Pinitial

DV = Vfinal - Vinitial

DT = Tfinal - Tinitial

even though they took different paths.

9

Chapter 1 / Thermochemistry

1.3 Introduction to Thermodynamics

First law of thermodynamics – energy can be converted from one form to another, but

cannot be created or destroyed.

DEsystem + DEsurroundings = 0

or

DEsystem = -DEsurroundings

constant

C3H8 + 5O2 3CO2 + 4H2O

S + O2 SO2

10

system surroundings

Chapter 1 / Thermochemistry

1.3 Introduction to Thermodynamics

The internal energy of a system has two components: kinetic energy of all motions and

potential energy of electrons and nuclei.

It is impossible to measure all these contributions accurately, so we cannot calculate the

total energy of a system with any certainty.

The change in E only can be measured, for a system when moves from initial state to

the final state.

DE = Ef - Ei

11

Chapter 1 / Thermochemistry

1.3 Introduction to Thermodynamics

DE = q + w

ΔE is the change in internal energy of a system

12

Chapter 1 / Thermochemistry

1.3 Introduction to Thermodynamics

13

Chapter 1 / Thermochemistry

1.3 Introduction to Thermodynamics

One way to illustrate mechanical work is to study the expansion or compression of a

gas.

DV > 0

DE = q + w

-PDV < 0

w = -P DV

wsys < 0

D E = q + w = q –p DV

Work is

not a

state

function!

Dw = wfinal - winitial

14

initial final

Chapter 1 / Thermochemistry

1.3 Introduction to Thermodynamics

constant temperature. What is the work done in joules if the gas expands (a)

against a vacuum and (b) against a constant pressure of 3.7 atm?

w = -P ΔV

W = -0 x 3.8 = 0 L•atm

To convert to joule x101.3

101.3 J

w = -14.1 L•atm x = -1430 J 15

1L•atm

Chapter 1 / Thermochemistry

1.4 Enthalpy of Chemical Reactions

DE = q + w

At constant pressure:

q = DH and w = -PDV

DE = DH - PDV

DH = DE + PDV

16

Chapter 1 / Thermochemistry

1.4 Enthalpy of Chemical Reactions

Enthalpy (H) is used to quantify the heat flow into or out of a system in a process

that occurs at constant pressure.

DH = H (products) – H (reactants)

DH = heat given off or absorbed during a reaction at constant pressure

17

DH < 0 (Exothermic) DH > 0 (Endothermic)

Chapter 1 / Thermochemistry

1.4 Enthalpy of Chemical Reactions

Thermochemical Equations

Is DH negative or positive?

Endothermic

DH > 0

6.01 kJ are absorbed for every 1 mole of ice that melts at 00C and 1 atm.

18

Chapter 1 / Thermochemistry

1.4 Enthalpy of Chemical Reactions

Thermochemical Equations

Is DH negative or positive?

Exothermic

DH < 0

250C and 1 atm.

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

19

Chapter 1 / Thermochemistry

1.4 Enthalpy of Chemical Reactions

Thermochemical Equations

• The stoichiometric coefficients always refer to the number of moles of a

substance

• If you reverse a reaction, the sign of DH changes

• If you multiply both sides of the equation by a factor n, then DH must change

by the same factor n.

20

Chapter 1 / Thermochemistry

1.4 Enthalpy of Chemical Reactions

Thermochemical Equations

• The physical states of all reactants and products must be specified in

thermochemical equations.

Example: How much heat is evolved when 266 g of white phosphorus (P4)

burn in air?

P4 (s) + 5O2 (g) P4O10 (s) DH = -3013 kJ

From equation:

1 mol P4 -------> 3013 kJ

2.15 mol P4 ----------> ?

21

2.15 x 3013 = 6468.6 kJ

Chapter 1 / Thermochemistry

1.4 Enthalpy of Chemical Reactions

PV = nRT

PDV = DnRT

number of moles of gases in reactants .

DH = DE + DnRT

PLEASE REMEMBER:

DH and DE given in KJ

The term DnRT in J

Chapter 1 / Thermochemistry

1.4 Enthalpy of Chemical Reactions

Example: The heat of combustion at constant volume of CH4 (g) is measured in bomb

calorimeter at 25C and is found to be –88.5 KJ / mol, what is DH?

CH4 (g) + 2O2 (g) CO2 (g) + 2HO2 (l), DE = -88.5 KJ / mol

Dn =1-(2+1) = -2

DH = DE + Dn RT

DH = -88.5 + (-2)(8.314X298)

1000

= -89.5 KJ

Chapter 1 / Thermochemistry

1.5 Calorimetry

The specific heat (s) of a substance is the amount of heat (q) required to raise the

temperature of one gram of the substance by one degree Celsius.

The heat capacity (C) of a substance is the amount of heat (q) required to raise the

temperature of a given quantity (m) of the substance by one degree Celsius.

C=mxs

q = m x s x Dt

q = C x Dt

Dt = tfinal - tinitial

24

Chapter 1 / Thermochemistry

1.5 Calorimetry

Example: How much heat is given off when an 869 g iron bar cools from 940C

to 50C?

s of Fe = 0.444 J/g • 0C

Dt = tfinal – tinitial = 50C – 940C = -890C

25

Chapter 1 / Thermochemistry

1.5 Calorimetry

reactions

Constant-Volume Calorimetry

qsys = qwater + qbomb + qrxn

qsys = 0

qwater = m x s x Dt

qbomb = Cbomb x Dt

26

No heat enters or leaves!

Chapter 1 / Thermochemistry

1.5 Calorimetry

Constant-Volume Calorimetry

Example: A quantity of 1.435 g of naphthalene (C10H8), a pungent-smelling substance used in

moth repellents, was burned in a constant-volume bomb calorimeter. Consequently, the

temperature of the water rose from 20.28°C to 25.95°C. If the heat capacity of the bomb plus

water was 10.17 kJ/°C, calculate the heat of combustion of naphthalene?

qcal = Ccalx Dt

= (10.17 kJ/°C) (25.95°C - 20.28°C)

= 57.66 kJ

qrxn = - (qwater + qbomb)

= - qcal

= -57.66 kJ

27

Chapter 1 / Thermochemistry

1.4 Enthalpy of Chemical Reactions

Example: A bomb type calorimeter used to measure the heat evolved by the combustion of

glucose C6H12O6

C6H12O6 (s) + 6O2(g) 6CO2(g) +6 H2O (l)

A 3.0 g sample of glucose is placed in bombs which is then filled with oxygen gas under

pressure . The bomb is placed in wall insulated colorimeter vessel that is filled with 1.20

kg of water the initial temperature of the assembly is 19.00C . The reaction mixture is

ignited by the electrical heating of a wire within the bomb . The reaction causes the

temperature of the calorimeter and its contents to increase to 25.50C . The heat

capacity of the calorimeter is 2.21 kJ / C .How much heat is evolved by the combustion

of 1 mol of glucose ?

Mass of C6H12O6 =3 g, mass of water = 1.2kg, T1=19 °C, T2= 25.5 °C, Ccal= 2.21 kJ

sH2O = 4.184 J/g °C, qrxn at 1mol of C6H12O6 =?

28

Chapter 1 / Thermochemistry

1.4 Enthalpy of Chemical Reactions

Mass of C6H12O6 =3 g, mass of water = 1.2kg, T1=19 °C, T2= 25.5 °C, Ccal= 2.21 kJ/°C

sH2O = 4.184 J/g °C, qrxn at 1mol of C6H12O6 =?

qrxn = Ctotal x Δt

Ctotal = Ccal + CH2O

CH2O = m x s = (1.2 x1000 ) x 4.184 = 5016 J/°C = 5.016 kJ/°C

Ctotal = 2.21 + 5.016 = 7.226 kJ/°C

qrxn = 7.226 x (25.5 -19)= 47 kJ

This q is for 3 g of C6H12O6 what is q for 1 mole

n = g/mwt = 3 / 180 = 0.017 mol

0.017 mol -------- 47 kJ

1 mol ------------- ? Kj

1 x 47 /0.017 = 2764.7 kJ

29

Chapter 1 / Thermochemistry

1.5 Calorimetry

Constant-Pressure Calorimetry

qsys = 0

qwater = m x s x Dt

qcal = Ccal x Dt

Reaction at Constant P

DH = qrxn

Chapter 1 / Thermochemistry

1.5 Calorimetry

Constant-Pressure Calorimetry

Example: A lead (Pb) pellet having a mass of 26.47 g at 89.98°C was placed in a constant-

pressure calorimeter of negligible heat capacity containing 100.0 g of water. The water

temperature rose from 22.50°C to 23.17°C. What is the specific heat of the lead pellet, if the

specific heat of water is 4.184 J/g.°C ?

qsys = qwater + qcal + qrxn qPb = m x s x Dt

qsys = 0 qPb

s=

m x Dt

qrxn = - (qwater + qcal)

-280.3 J

qrxn = - qwater s=

26.47g x (23.17 °C – 89.98 °C)

qPb = - qwater

qwater = m x s x Dt s= 0.158 J/g.°C

= (100.0 g) (4.184 J/g.°C) (23.17°C -22.50°C)

= 280.3 J

qPb = - 280.3 J 31

Chapter 1 / Thermochemistry

1.5 Calorimetry

How much heat is liberated when 36.0 g of Al, reacts with excess Fe2 O3 ?

From equation

2 mole Al ----- 848 kJ

1.33 mol ----- ? kJ

1.33 x 848 / 2 = 563.9 kJ

32

Chapter 1 / Thermochemistry

1.5 Calorimetry

33

Chapter 1 / Thermochemistry

1.6 Standard Enthalpy of Formation and Reaction

substance, must I measure the enthalpy change for every reaction of interest?

reference point for all enthalpy expressions. f

Standard enthalpy of formation (DH0) is the heat change that results when one

f

mole of a compound is formed from its elements at a pressure of 1 atm.

The standard enthalpy of formation of any element in its most stable form is

zero.

DH0 (O2) = 0 DH0 (C, graphite) = 0

f f

DH0 (O3) = 142 kJ/mol DH0 (C, diamond) = 1.90 kJ/mol

f f

34

Chapter 1 / Thermochemistry

1.6 Standard Enthalpy of Formation and Reaction

35

Chapter 1 / Thermochemistry

1.6 Standard Enthalpy of Formation and Reaction

The standard enthalpy of reaction (DH0 ) is the enthalpy of a reaction carried out

rxn

at 1 atm.

aA + bB cC + dD

rxn f f f f

rxn f f

Fe2O2(s) + 3CO (g) 2Fe(s) + 3CO2 (g)

DH = 3DHf CO2 (g) – [DHf Fe2 O3(s) + 3 DHf CO(g) ]

= 3 ( -393.5 KJ ) – [ -(822.2 KJ ) + 3 ( -110.5 KJ)]

= - 26.8 KJ

36

Chapter 1 / Thermochemistry

1.6 Standard Enthalpy of Formation and Reaction

Example: Benzene (C6H6) burns in air to produce carbon dioxide and liquid water.

How much heat is released per mole of benzene combusted? The standard enthalpy of

formation of benzene is 49.04 kJ/mol.

rxn f f

rxn f f f

rxn

-5946 kJ

= - 2973 kJ/mol C6H6

2 mol

37

Chapter 1 / Thermochemistry

1.6 Standard Enthalpy of Formation and Reaction

OF2(g) + H2O (g) O2(g) + 2HF(g)

IF DH˚f O F2(g) = 23 KJ / mol, DH˚f H2O(g) = -241.8 KJ/ mol, DH˚f HF(g) = -268.6 KJ / mol

= 2 DH°f HF(g) – [ DH°f OF2(g) - DH˚f H2O (g)]

= 2( -268.6) –[ 23 –241.8]

= -318.4KJ

DH = DE + DnRT

Dn = 3- 2 = 1

-318.4 = DE +( 1x8.314x298) /1000

= DE + 2.48

DE = -318.4 –2.48 = -320KJ

38

Chapter 1 / Thermochemistry

1.6 Standard Enthalpy of Formation and Reaction

Hess’s Law: When reactants are converted to products, the change in enthalpy

is the same whether the reaction takes place in one step or in a series of steps.

(Enthalpy is a state function. It doesn’t matter how you get there, only where

you start and end.)

39

Chapter 1 / Thermochemistry

1.6 Standard Enthalpy of Formation and Reaction

CO (g) + 1/2O2 (g) CO2 (g)

C (graphite) + O2 (g) CO2 (g)

40

Chapter 1 / Thermochemistry

1.6 Standard Enthalpy of Formation and Reaction

Example: Calculate the standard enthalpy of formation of CS2 (l) given that:

C(graphite) + O2 (g) CO2 (g) ΔH0 = -393.5 kJ

rxn

S(rhombic) + O2 (g) SO2 (g) ΔH0 = -296.1 kJ

rxn

CS2(l) + 3O2 (g) CO2 (g) + 2SO2 (g) ΔH0 = -1072 kJ

rxn

1. Write the enthalpy of formation reaction for CS2

41

Chapter 1 / Thermochemistry

1.6 Standard Enthalpy of Formation and Reaction

2. Add the given rxns so that the result is the desired rxn.

rxn

rxn

42

Chapter 1 / Thermochemistry

1.6 Standard Enthalpy of Formation and Reaction

4NH3 (g) + 3O2 (g) 2N2 (g) + 6H2O (l) , DH = - 1531 kJ (1)

N2O(g) + H2 (g) N2(g) + H2O (l) , DH = - 367.4kJ (2)

H2(g) + ½ O2 (g) H2O(g) , DH = - 285.9 kJ (3)

(4/2)NH3 (g) + (3/2)O2 (g) (2/2)N2 (g) + (6/2)H2O (l) , DH = - 1531/2 kJ (1)

3N2O(g) + 3H2 (g) 3N2(g) + 3H2O (l) , DH = - 367.4 x3 kJ (2)

3H2O(g) 3H2(g) + ½ x3 O2 (g) DH = + 285.9 x3 kJ (3)

ΔH = - 1531/2 + (- 367.4 x3 ) + (285.9 x3) = -1010 kJ 43

rxn

Chapter 1 / Thermochemistry

1.6 Standard Enthalpy of Formation and Reaction

Atoms are held together in molecules by chemical bonds. The energy required to break the

bond that holds two atoms together in a diatomic molecules is called bond dissociation energy.

H – H (g) 2H(g) , DH = + 435 KJ

Cl – Cl (g) 2Cl ( g ) , DH= + 243 KJ

H-Cl (g) H(g) + Cl (g), DH= + 431 KJ

The reverse of bond dissociation energy is -ve (because it forms bonds)

DH for any reaction can be calculated from bond energies dissociation of reactant

and product

Since the reaction is the breaking of bonds for reactants and forms bonds for

products

DHrxn=S bond energies of reactants -S bond energies of products

44

Chapter 1 / Thermochemistry

1.6 Standard Enthalpy of Formation and Reaction

H-F 565 N-Cl 201

H-Cl 431 P-CL 326

H-Br 364 C-C 347

H-l 297 C=C 619

F-F 155 CC 812

Cl-Cl 243 C-H 414

Br-Br 193 C-O 335

l-l 151 C=O 707

O-O 138 C-F 485

O2b 494 C-Cl 326

O-H 463 C-N 293

O-F 183 C=N 616

O-Cl 205 CN 879

N-N 159 S-H 339

N=N 418 S-S 213

NN 914 S-Cl 276

N-H 389

45

Chapter 1 / Thermochemistry

1.6 Standard Enthalpy of Formation and Reaction

Example: Use the average board energies to calculate the value of for the reaction

In the reactants in Product

6 bonds of N-H One bond of N≡N

3 bonds of cl-cl 6 bond of H- Cl

DH = 6 ( N-H ) + 3 ( Cl – Cl ) – [ N N +6( H – Cl) ]

= 6 ( 389 ) + 3 ( 243 ) – [ 941 + 6 ( 431) ]

= - 464 KJ

46

Chapter 1 / Thermochemistry

1.7 Heat of Solution and Dilution

The enthalpy of solution (DHsoln) is the heat generated or absorbed when a certain

amount of solute dissolves in a certain amount of solvent.

DHsoln = Hsoln - Hcomponents

melting ice?

a cold pack?

47

Chapter 1 / Thermochemistry

1.7 Heat of Solution and Dilution

Chapter 1 / Thermochemistry

1.4 Enthalpy of Chemical Reactions

49

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