Thermo chemistry

CHAPTER 6

DR. SULTANA BEDOURA

 Lecture Plan 2
 Energy
 Energy change in chemical reaction
 Exothermic and endothermic processes
 The first law of thermodynamics
 Work, heat and internal energy
 Enthalpy
 Thermochemical equation
 Calorimeter
 Hess’s Law
 Enthalpy of solution
 Energy 3
 Energy is the capacity to do work
Radiant energy : comes from the sun and is earth’s primary energy source
Thermal energy : associated with the random motion of atoms and molecules
Chemical energy: the energy stored within the bonds of chemical substances
Nuclear energy : the energy stored within the collection of neutrons and protons
in the atom
Potential energy : the energy available by virtue of an object’s position

 Law of conservation of energy

“The total quantity of energy in the universe is assumed constant”
 Heat and Thermochemistry 4
 Almost all chemical reactions absorb or produce (release) energy, generally in
the form of heat
 Heat is the transfer of thermal energy between two bodies that are at different
temperatures
 Temperature is a measure of the thermal energy
 Thermochemistry is the study of heat change

in chemical reactions
 When heat is absorbed or released during a process,

energy is conserved, but it is transferred between This infrared photo shows where
energy (heat) leaks through the house.
system and surroundings The more red the color, the more
energy is lost to the outside
 The Systems and Surroundings
5
 The system is the specific part of the universe that is of interest in the study
 The surroundings are the rest of the universe outside the system
 Three types of systems:
Water vapor

Heat Heat

Open system Closed system Isolated system

Allows the exchange of Allows the exchange of Allows neither
both energy and mass energy but not mass energy nor mass
with surroundings To be exchanged
 Exothermic and Endothermic6

Processes
Exothermic process : The process that gives off heat – transfers thermal energy
from the system to the surroundings of interest in the study
2H2 (g) + O2 (g) 2H2O (l) + energy
H2O (g) H2O (l) + energy
 Endothermic process : The process in which heat has to be supplied to the system
from the surroundings
energy + 2HgO (s) 2Hg (l) + O2 (g)
energy + H2O (s) H2O (l)
 Exothermic : Heat released, System surroundings
 Endothermic: Heat absorbed, System surroundings
 Thermodynamics 7
 Thermodynamic: The scientific study of the interconversion of heat and other kinds
of energy
 State functions : Properties that are determined by the state of the system,
regardless of how that condition was achieved.
E.g. energy, pressure, volume, temperature

∆E = Efinal – Einitial
∆P = Pfinal – Pinitial
∆V = Vfinal – V initial
Paths (Blue and red) are different though the
∆T = Tfinal – Tinitial potential energy of two hikers is same
 First Law of Thermodynamics8
 Energy can be converted from one form to another, but cannot be created or
destroyed
∆Esystem + ∆Esurroundings = 0
∆Esystem = - ∆Esurroundings

C3H6 + 5O2 3CO2 + 4H2O + energy

Chemical energy lost by combustion = energy gained by the surroundings

 First Law of Thermodynamics9
 Another form of first law of thermodynamics, ∆E = q + w
• ∆E is the change in internal energy of a system, a state function
• q is the heat exchange between the system and the surroundings
• w is the work done on (or by) the system
• w = -P∆V , when a gas expands against a constant external pressure
Table: Sign Conventions for Work and Heat
Process In brief Sign
•Work done by the system on surroundings System works ─
•Work done on the system by surroundings Surroundings work +
•Heat absorbed by the system from the surroundings Endothermic process +
•Heat absorbed by the surroundings from the system Exothermic process ─
 Work (w) and Heat (q) 10
 Work and Heat

Work Heat
• Work (w) = force (f) x distance (d)  Heat is kind of energy, q = ∆E – w
• Work done by gas on the  Describes about the process
surrounding is, w = - P ∆V  Temperature is the measure of heat
∆V > 0; -P ∆V < 0; wsys < 0
• -P ∆V =(F/ d2 )x d3 = F x d = W  Temperature and heat is not same
• Not a state function Not a state function
• w = wfinal – w initial  q = q final – q initial
• Unit : joules (J) Unit: joules (J)
 Class work 11
 The work done when a gas is compressed in a cylinder is 462 J. During this
process, there is a heat transfer of 128 J from the gas to the surroundings.
Calculate the energy change for this process.

∆E = q + w

= -128 J + 462 J

= 334 J
 Class work 12
 A gas expands and does P - V work on the surroundings equal to 325 J. At the
same time, it absorbs 127 J of heat from the surroundings. Calculate the change
in energy of the gas.

∆E = q + w

= 127 J - 325 J

= -198 J
 Class work 13
 A sample of nitrogen gas expands in volume from 1.6 L to 5.4 L at 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?
∆V = 5.4 L – 1.6 L = 3.8 L
(a) Given , P = 0
w = - P∆V = 0 x 3.8 = 0 j
(b) Given , P = 3.7 atm
w = - P∆V
= -3.7 atm x 101.325 X 103
Pa 1
x 3.8 L x 3m 3

1 atm 10 L
= -1424.6 Pa.m3 = - 1424.6 j
Internal Energy and the First Law 14

of TD
How first law of TD can be applied to processes carried out under different
conditions
 Two situations most commonly encountered in the laboratories:
• Pressure on the system kept constant:
∆E = q - P ∆V
• Volume of the system kept constant:
∆E = q + w
= qv − P ∆V
= qv [∆V = 0 ]
 When the process is so rapid :
Assume no heat exchange occurs between the system and its surroundings;
∆E = q + w = 0  w [q = 0]
 Enthalpy 15
 Enthalpy (H): The amount of heat content used or released in a system at
constant pressure. 
 Expressed as the change in enthalpy. (ΔH)
 ΔH = H (products) – H (reactants)
 Heat used/consumed: endothermic: ΔH> 0
 Heat released/ produced: exothermic: ΔH<0
 Unit(SI): Joules/ Calorie [1 cal = 4.184 J]
 ΔH is a state function
Enthalpy & the First Law of TD
16
 First Law of Thermodynamics: E = q + w
 At constant pressure:
E = qP – PV
qP = E + PV….. (1)
 For Enthalpy (H) a new function:
H = E + PV
H = E +  (PV) @ constant P
H = E + PV….. (2)
 From (1) & (2)  H = qP
 Enthalpy : quantify the heat flow into or out of a system that occurs at constant pressure
 ΔH is a state function. Whereas qp is not state function
 A Comparison of ∆H and ∆ E17
2Na(s) + 2H2O(l) 2NaOH (aq) + H2(g) H = -367.5 kJ/mol
Assumption: T = 250C and V is negligible
Then, @ 1 atm and 25 oC, 1 mole H2 = 24.5 L
-PV = -1 atm x 24.5 L = -2.5 kJ
 E =  H - PV = -367.5 kJ/mol – 2.5 kJ/mol = -370.0 kJ/mol
 ΔH and ΔE are approximately same.
 In above reaction, the ΔH is smaller than ΔE
as some internal energy released to do gas expansion work.
 For reactions that do not involve gases, ΔH = ΔE.
 For ideal gases,
ΔE = ΔH – Δ(PV) = ΔH- Δ (nRT)
= ΔH- RT Δn [Δn = number of moles in product- number of moles in reactants]
 Thermochemical Equations18
 In a chemical reaction two changes occur-

1. Chemical change
P4(s) + 5O2(g)  P4O10(s) ; ∆H = -3013 KJ/mol

2. Physical change
H2O (s)  H2O (l) ; ∆H = 6.01 KJ/mol
H2O (l)  H2O (g); ∆H = 6.01 KJ/mol
 Thermochemical Equations19
 H = heat given off or absorbed during a reaction at constant pressure

•System absorbs heat •System gives off heat

•Endothermic •Exothermic
•Hproducts > Hreactants •Hproducts < Hreactants
•H > 0 •H < 0

• 6.01 kJ are absorbed for every 1 mole of ice that • 890.4 kJ are released for every 1 mole of methane that is
melts at 00C and 1 atm combusted at 250C and 1 atm
H 2O ( s) H2O (l) H = 6.01 kJ/mol CH4 (g) + 2O2 (g)  CO2 (g) + 2H2O (l) ;  H = -890.4 kJ/mol
 Thermochemical Equations20
 The The stoichiometric coefficients always refer to the number of moles of a
substance: H 2O ( s ) H2O (l) ΔH = 6.01 kJ/mol
 If you reverse a reaction, the sign of ΔH changes:

H2O (l) H2O (s) ΔH = -6.01 kJ/mol

 If you multiply both sides of the equation by a factor n, then ΔH must change by
the same factor n:
2H2O (s) 2H2O (l) ΔH = 2 x 6.01 = 12.0 kJ
 The physical states of all reactants and products must be specified in
thermochemical equations
H2O (s) H2O (l) ΔH = 6.01 kJ/mol
H2O (l) H2O (g) ΔH = 44.0 kJ/mol
 Class Work 21
 How much heat is evolved when 266 g of white phosphorus (P4) burn in air?
P4 (s) + 5O2 (g) P4O10(s) ΔH = - 3013 kJ/mol

x 1 mol P x -3013 kJ = -6470 kJ

266 g P4 4
1 mol P4
123.9 g P4
 Specific Heat & Heat Capacity
22
 The specific heat (s) of a substance: The amount of heat (s) required to raise the
temperature of 1 gram of the substance by one degree Celsius.
unit: J/g . °C
Heat (q) absorbed or released: q = m x s x ∆t where , ∆t = tfinal – tinitial

 The heat capacity (C) of a substance: The amount of heat (q) required to raise the
temperature of given quantity (m) of the substance by one degree Celsius. C
=mxs
Unit: J/ °C
Heat (q) absorbed or released: q = C x ∆t where , ∆t = tfinal – tinitial
 Class Work 23
 How much heat is given off when an 869 g iron bar cools from 94oC to 5oC?

s of Fe = 0.444 J/g • oC
t = tfinal – tinitial = 5oC – 94oC = –89oC

q = ms  t = 869 g x 0.444 J/g • oC x –89oC

= –34,000 J
 Calorimetry 24
 Calorimetry is the act of measuring the heat change of chemical
reactions or physical changes

 Calorimeter is the specifically designed closed container

 We will discuss two different types of calorimeters-

1. Constant-volume calorimeter
2. Constant-pressure calorimeter
Constant-Pressure Calorimeter
25

qsys = qwater + qbomb + qrxn

qsys = 0
qrxn = - (qwater + qbomb)
qwater = m x s x t
qbomb = Cbomb x  t
Reaction at Constant V
 H = qrxn
 H ~ qrxn

No heat enters or leaves!

Constant-Volume Calorimeter
26

qsys = qwater + qcal + qrxn

qsys = 0
qrxn = - (qwater + qcal)
qwater = m x s x t
qcal = Ccal x t
Reaction at Constant P
H = qrxn

No heat enters or leaves!

 Heat of Typical Reaction at 27
 Heats of some reactionsConstant P
measured at constant pressure
Standard Enthalpy of Formation
28
 As there is no way to measure the absolute value of the enthalpy of a substance,
must measure the enthalpy change for every reaction of interest
 Establish an arbitrary scale with the standard enthalpy of formation (Hf0) as a
reference point for all enthalpy expressions
 Standard enthalpy of formation (Hf0) is the heat change that results when one
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
H0 (O2) = 0  H0 (C, graphite) = 0
f f
 H0 (O3) = 142 kJ/mol  H0 (C, diamond) = 1.90 kJ/mol
f
 Standard enthalpy of reaction: For aA + bB  cC +f dD

H0 = [ c H0 (C) + d H0 (D) ] - [ a H0 (A) + b H0 (B) ]

rxn f f f f
 Hess’s law 29
 When reactants are converted to products, the change in the enthalpy is same
whether the reaction takes place in one step or in a series of steps.
 Enthalpy is a state function, it does not matter how you got there, only where you
start and end.
Hx
A+B C+D

H1 H2

Intermediate
Products

Hx = H1 + H2

Standard Enthalpy of Formation
30

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

CO(g) + 1/2O2(g) CO2(g)
C(graphite) + 1/2O2(g)  CO(g) ?

C(graphite) + O2(g)  CO2(g)

+ CO2(g)  CO(g) + 1/2O2 (g)
C(graphite) + 1/2O2(g)  CO(g)

H0f (CO) = − 110.5 kJ/mol

 Class Work 31
 From these data, calculate the enthalpy change for the transformation

S(rhombic)  S(monoclinic)
S(rhombic) + O2(g)  SO2(g) ΔH°rxn = -2296.06 kJ/mol
S(monoclinic) + O2(g)  SO2(g) ΔH°rxn = -2296.36 kJ/mol
(Monoclinic and rhombic are different allotropic forms of elemental sulfur)

S(rhombic) + O2(g)  SO2(g) ΔH°rxn = -2296.06 kJ/mol

(+) SO (g)  S(monoclinic) + O (g) ΔH°rxn = 2296.36 kJ/mol
2 2

S(rhombic)  S(monoclinic) ΔH°rxn = 0.30 kJ/mol

 Problem 32
 Calculate the standard enthalpy of formation of CS2 (l) given that:

C(graphite) + O2 (g) CO2 (g) H0 rxn= -393.5 kJ/mol

S(rhombic) + O2 (g) SO2 (g) H0 rxn= -296.1 kJ/mol
CS2(l) + 3O2 (g) CO2 (g) + 2SO2 (g) H0 rxn= -1072 kJ/mol

1. Write the formation reaction for CS2

C(graphite) + 2S(rhombic) CS2 (l)

 Problem (cont ) d
33
C(graphite) + 2S(rhombic) CS2 (l)

2. Add the given rxns so that the result is the desired rxn.
C(graphite) + O2 (g) CO2 (g) H0 rxn= -393.5 kJ/mol
2 S(rhombic) + 2O (g) 2SO (g) H0 rxn= -296.1 kJ/mol X2
2 2
(+) CO (g) + 2SO2 (g) CS2 (l) + 3O2 (g) H0 rxn= +1072 kJ/mol
2

C(graphite) + 2S(rhombic) CS2 (l)

rxn
H0 = -393.5 + (2x-296.1) + 1072 = 86.3 kJ/mol
 Problem 34
 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, water and CO2 is 49.04 kJ/mol, -187.6 kJ/mol and -393.5
kJ/mol respectively.
2C6H6 (l) + 15O2 (g) 12CO2 (g) + 6H2O (l)

H0 rxn =  nHf0 (products) -  mHf0 (reactants)

H0 rxn = [12 Hf0 (CO2) + 6 Hf0 (H2O)] – [ 2 Hf0 (C6H6)]
H0 rxn = [12 x – 393.5 + 6 x -187.6] – [2 x 49.04] = - 5946 KJ
Heat released per mole of benzene = ( -5946 KJ) / 2 mol
 Problem 35
 Calculate the standard enthalpy of formation of C2H2 from its elements:

2C(graphite) + H2 (g) C2H2 (g)

The equations for each step and the corresponding enthalpy changes are
(a) C(graphite) + O2(g) CO2 (g) H0 rxn
= -393.5 kJ/mol
(b) H2(g) + 1/2O2 (g) H2O (l) H0 rxn
= -285.8 kJ/mol
(c) 2C2H2(g) + 5O2 (g) 4CO2 (g) + 2H2O (l) H0 rxn= -2598.8kJ/mol
ax4 4C(graphite) + 4O2(g) 4CO2 (g) H0rxn = 4 x -393.5 kJ/mol
cx-1 4CO2 (g) + 2H2O (l) 2C2H2(g) + 5O2 (g) H0rxn =-1x -2598.8 kJ/mol
(+)
bx2 2 H2(g) + O2 (g) 2H2O (l) H0rxn = 2x -285.8 kJ/mol
4C(graphite) + 2H2 (g) 2 C2H2 (g) H0rxn rxn
= 453.2 kJ/mol
 Enthalpy of Solution 36
 The enthalpy of solution ( Hsoln) is the heat generated or absorbed when a
certain amount of solute dissolves in a certain amount of solvent.
Heats of solution of some
Ionic compounds
1. Which substance(s) could be used for melting ice?
2. Which substance(s) could be used for a cold pack?

Given, Hsoln = Hsoln - Hcomponents

The Solution Process for NaCl
37

Hsoln = Step 1 + Step 2 = 788 – 784 = 4 kJ/mol

Thank You