Thermochemistry

Walaiporn Prissanaroon-Ouajai
Department of Industrial Chemistry
KMUTNB
Thermochemistry
The study of energy changes that occur during
chemical reactions or phase changes.

If the process absorbs energy Endothermic reaction

If the process releases energy Exothermic reaction

 Thermochemistry
First law of Thermodynamics
Calorimetry
Enthalpy of formation
Enthalpy of reaction

Bond energy
Walaiporn Prissanaroon-Ouajai, IC, KMUTNB
 Forms of Energy
Potential energy (PE) Kinetic energy (KE)
Chemical Electromagnetic
Gravitational Thermal
Nuclear Sound
Elastic Electrical
Motion
Conservation of energy
Energy cannot be created or destroyed,
it can only be transformed.

Walaiporn Prissanaroon-Ouajai, IC, KMUTNB

 Energy transformation

Walaiporn Prissanaroon-Ouajai, IC, KMUTNB www.otoanahtar.com.tr

 Describe steps of energy transformation
in power plant.

Coal-fired power plant

System and Surrounding
Surrounding

System

System + Surrounding = Universe

Walaiporn Prissanaroon-Ouajai, IC, KMUTNB
System and Surrounding E = Efinal - Einitial

Endothermic reaction Exothermic reaction

Absorb Release
Energy from Energy to
surrounding surrounding
System System

Esystem = + Esystem = -
Esurrounding = Esurrounding =
 First Law of Thermodynamics

Conservation of energy
Energy cannot be created or destroyed,
it can only be transformed.
Walaiporn Prissanaroon-Ouajai, IC, KMUTNB
 Internal energy, U
For substances, U is the energy associated with electronic and
intramolecular forces of molecules.
Kinetic energy Potential energy
U = KE PE Translation motion O H H
H
O
Rotational motion H

U Temp Chemical bonding

Vibrational motion Intermolecular force

Walaiporn Prissanaroon-Ouajai, IC, KMUTNB

First Law of Thermodynamics
q In closed system
U of a system is affected by two variables.
W
Initial Final Usys qsys Wsys
total change in heat exchanged work done
internal energy between a system by or on
of a system and its surroundings the system.
https://byjus.com/jee/first-law-of-thermodynamics/
Heat (q) Energy flowing from one material to another
spontaneously due to their temperature difference.

High energy Endothermic reaction (q = )

Hot
Exothermic reaction (q = )
Heat Warm
flow Thermal equilibrium Unit : Joule or calorie
1 cal = 4.184 J
Cold Low energy
Walaiporn Prissanaroon-Ouajai, IC, KMUTNB
Work (W) expansion work of gas (system)
Pext Pext
Wgas = -Pext V

V
Pgas Pgas Unit of work : ?

***Unit conversion
L.atm = J cal
1 cal = 4.184 J Walaiporn Prissanaroon-Ouajai, IC, KMUTNB
 Gas Expansion Wgas = -Pext V Gas Compression
Pext Pext Pext Pext

Pgas Pgas
Pgas Pgas
(Vf > Vi) V = + (Vi > Vf) V = -
W = W =
work is done by system work is done by surrounding
(or work is gained by system)
Predict the sign of W
W = -Pext V
Hg(l) Hg(g)

3O2(g) 2O3(g)

2C2H6(g) + 7O2(g) 4CO2(g) + 6H2O(g)

A system of gas expands from mL to mL at a constant
temperature and pressure of atm, calculate work in joule.

W = -85.09 J
 3000 J of heat is added to a system and 2500 J of work is done
by the system. What is the change in internal energy (in joule) of the
system?

Walaiporn Prissanaroon-Ouajai, IC, KMUTNB U = +500 J

Thermodynamic Processes U = q + W
U = q - Pext V
Adiabatic Process (q

Isothermal Process T = U =

. Bomb Calorimeter const. V V

Walaiporn Prissanaroon-Ouajai, IC, KMUTNB

Different ways to obtain heat of reaction (q)
U q W

q 1. Specific heat (s)

2. Calorimetry
3. Thermochemistry At constant pressure,
H 4. Hess s law
5. Bond Energy
H = q
H = qP
Walaiporn Prissanaroon-Ouajai, IC, KMUTNB
specific heat

Walaiporn Prissanaroon-Ouajai, IC, KMUTNB

Specific heat (s)
s = amount of heat (q) to be supplied to a given 1 g of a
H2O 1 g material to increase 1 K (or C) of temperature.
Note: T = +1oC = +1K
s Unit: cal/g.K or J/g.K

q = ms T

s of water = 1 cal/g.K

Walaiporn Prissanaroon-Ouajai, IC, KMUTNB

Let s check out T in oC and T in K

27 oC 57 oC

T in oC T in K
 g (Specific Heat, s)
s J/g.K q =
1 g

amount of heat
(q) for J/mol.K q =
mole (Molar Heat Capacity, c) c
increasing 1 K
H2O 18 g
(or 1 10C)

Whole amount (Heat Capacity, C) C J/K q =

Used for the object consisting
of different materials Ex. Calorimeter
Walaiporn Prissanaroon-Ouajai, IC, KMUTNB
Find amount of heat (q) required to cool down 27 g of water
from 40 oC to 20 oC (Given s of water = 1 cal/g.K)

-540 cal
Walaiporn Prissanaroon-Ouajai, IC, KMUTNB
Specific heat of some substances
substance s (J/g-K) or Find amount of heat (q) required to heat up
(J/g-oC) the materials for 20 oC
Lead 0.128
Mercury 0.140
Copper 0.386 H2O 100 g
Zinc 0.387
Aluminum 0.900
Wood 1.70
Ice ( 10oC) 2.05
C2H5OH 2.40 Cu 100 g
Water 4.186
Walaiporn Prissanaroon-Ouajai, IC, KMUTNB
 A piece of unknown solid substance weighs 437.2 g, and requires 8460 J to
increase its temperature from 19.3 oC to 68.9 oC.
(a) What is the specific heat of the substance?
(b) Predict the material of this substance.

Walaiporn Prissanaroon-Ouajai, IC, KMUTNB

Calorimetry

Walaiporn Prissanaroon-Ouajai, IC, KMUTNB

 Calorimetry the process of measuring the amount of heat released or absorbed
(q) during a chemical reaction by observing the temperature change
( T) in the reaction.

Container T q
Insulator*
Thermometer qsystem qreaction qsolution qcalorimeter
Stirrer
Calorimeter Since qsystem 0
q = ms T
q = nc T qrxn = -(qsolution + qcalorimeter)
q = C T
Walaiporn Prissanaroon-Ouajai, IC, KMUTNB
 Two Types of Calorimeters
1. Adiabatic calorimeter
(Coffee-cup calorimeter)
Constant pressure
qp = qrxn = -(qsolution + qcalorimeter)

qp = H
Walaiporn Prissanaroon-Ouajai, IC, KMUTNB (Enthalpy, H)
Two Types of Calorimeters
2. Bomb calorimeter Constant V
Used for finding heat of combustion
qsystem qreaction qwater qcalorimeter
Since qsystem 0
qrxn = -(qwater + qcalorimeter) = qV
U = qv - Pext V
U = qv
 Calculation :
coffee-cup calorimeter

Walaiporn Prissanaroon-Ouajai, IC, KMUTNB

Find mixing temperature (or final temperature)
When 20 g of an aluminum rod at 98 oC is placed in 50 g of water at
20 oC in a coffee-cup calorimeter. What is the final temperature of the aluminum rod
Given
s of Al = 0.903 J/g.oC
s of H2O = 4.18 J/g.oC
Ccal = 0.5 J/oC

Walaiporn Prissanaroon-Ouajai, IC, KMUTNB

Find heat of reaction (qrxn) (in Coffee-cup calorimeter)
Dissolving g of NH4NO3 in g of water in a coffee cup calorimeter at oC causes the

temperature to reduce to oC
Given
1) What is the amount of heat involved in the dissolution? s of NH4NO3(aq) = s of H2O = 1 cal/g.K
2) Is the reaction exothermic or endothermic? Ccal = 0

1464.5 cal
endothermic
Walaiporn Prissanaroon-Ouajai, IC, KMUTNB
 Find heat of reaction (qrxn) (in Coffee-cup calorimeter)
When 50 mL of 1 M HCl(aq) and 50 mL of 1 M NaOH(aq), both at 22.0 oC, are added
to a coffee cup calorimeter, the temperature of the mixture reaches a maximum of 28.9 oC.
What is the approximate amount of heat produced by this reaction?
Given
Ccal = 0
s of NaCl(aq) = 4.184 J/g.oC
Density of NaCl(aq) = 1 g/mL

Walaiporn Prissanaroon-Ouajai, IC, KMUTNB 2.9 x 103 J

 Calculation :
bomb calorimeter

Walaiporn Prissanaroon-Ouajai, IC, KMUTNB

Find heat of reaction (qrxn) (in Bomb calorimeter)
When 3.12 g of glucose, C6H12O6, is burned in a bomb calorimeter, the temperature of
the calorimeter increases from 23.8 oC to 35.6 oC. The calorimeter contains 775 g of
water, and the bomb itself has a heat capacity of 893 J/oC.
How much heat (kJ/g) was produced by the combustion of the glucose ?
Given
s of water = 4.184 J/g.oC
Density of water = 1 g/mL

q = 15.6 kJ/g of glucose

Walaiporn Prissanaroon-Ouajai, IC, KMUTNB
Find heat of reaction (qrxn) (in Bomb calorimeter)
When 0.963 g of benzene, C6H6, is burned in a bomb calorimeter, the temperature of
the calorimeter increases by 8.39 oC. The bomb has a heat capacity of 784 J/oC and
is submerged in 925 mL of water. How much heat was produced by the combustion of
the glucose sample? Given
o
s of water = 4.184 J/g. C
Density of water = 1 g/mL

q = 40.5 kJ/g of benzene

Walaiporn Prissanaroon-Ouajai, IC, KMUTNB
 Enthalpy, H
Enthalpy change, H

Walaiporn Prissanaroon-Ouajai, IC, KMUTNB

 Enthalpy, H
Enthalpy is roughly equivalent to the amount of energy lost or gained
during the reaction at constant pressure.

H qP Endothermic reaction ( H = )
Exothermic reaction ( H = )

1st law of Thermodynamics U q W

Walaiporn Prissanaroon-Ouajai, IC, KMUTNB
Thermochemical equation
Chemical equation with given H
Exothermic reaction
C(s) + O (g CO (g kJ
C(s) O (g CO (g) H kJ

Endothermic reaction
2NH3 g + 91 kJ N (g H (g
2NH3 g N (g)+ H (g H = + kJ
H kJ/mol of NH3
 2CH3OH l) 3O2 g 2CO2 g 4H2O g kJ
Is this endothermic or exothermic reaction?
Find molar enthalpy of combustion of methanol (kJ/mol).
Find heat released from the combustion of g methanol.

1) Exothermic
H kJ mol
H kJ
Walaiporn Prissanaroon-Ouajai, IC, KMUTNB
 From 2C2H6 g) 7O2 g 4CO2 g 6H2O l H = -3112 kJ
Combustion of ethane releases some heat as above. If we want to heat 800 g of
water from oC to 98 oC, how many grams of ethane would be fed in
combustion process. (s of water = 4.184 J/g.K)

Walaiporn Prissanaroon-Ouajai, IC, KMUTNB

Calculation of H

Walaiporn Prissanaroon-Ouajai, IC, KMUTNB

Calculation of H

1. Enthalpy of formation
H 2.
3. Bond Energy

Walaiporn Prissanaroon-Ouajai, IC, KMUTNB

Standard Enthalpy of Formation
o
Hf

Walaiporn Prissanaroon-Ouajai, IC, KMUTNB

Standard Enthalpy of Formation
Hof Enthalpy change during the formation of 1 mole of the substance
from its elements at standard states. (1 atm, 25oC)

Any element in its most stable Hof

Ex. O2(g), H2(g), C(s), Na(s), Hg(l)

C(s ½O (g) CO(g Ho = -111 kJ Hof of CO(g -111 kJ/mol

C(s + O (g CO (g Ho kJ Hof of CO (g = -393 kJ/mol

Walaiporn Prissanaroon-Ouajai, IC, KMUTNB
Standard molar enthalpy of formation
Formation of butane
4C(s,graphite) +5H (g) C4H10(g
Ho -127.1 kJ
Formation of sucrose
12C(s,graphite)+11H2 g .5O g C12H22O11 s
Ho 2221.2 kJ

Walaiporn Prissanaroon-Ouajai, IC, KMUTNB @2003 Thomson-Brooks/Cole

From 4C s) 6H2 g O2 g 2C2H5OH l + 476.8 kJ
Find Hof of C2H5OH l in kJ/mol

Walaiporn Prissanaroon-Ouajai, IC, KMUTNB -238.4 kJ/mol

 Calculation of H of reaction from o
Hf
aA + bB cC + dD

Horxn Hof product) Hof reactant)

Horxn [c Hof C d Hof D ] [a Hof A b Hof B ]
Hf = Heat of formation
Hneut = Heat of neutralization
Hrxn Hfusion = Heat of fusion
Hsol = Heat of solution
Hcomb = Heat of combustion
Walaiporn Prissanaroon-Ouajai, IC, KMUTNB
 Find enthalpy change of the reaction:
NH3 g O2 g N2 g H2O g
(kJ/mol) NH3 (g) H2O (g)
Hof -46 -24

Walaiporn Prissanaroon-Ouajai, IC, KMUTNB kJ

 Find molar enthalpy change (kJ/mol) of the combustion of CH4
(kJ/mol) CH4 (g) CO2 (g) H2O (g)
Hof -7 -393.5 -24

802 kJ/mol
Walaiporn Prissanaroon-Ouajai, IC, KMUTNB
 Al s Fe2O3 s Al2O3 s + 2Fe(l)
Calculate the heat released in kilojoules per gram of Al reacted with Fe2O3.
(kJ/mol) Fe2O3 s Al2O3 s Fe(l)
Ho f -822 -1670 12.40
AW of Al = 27 g/mol

-15.25 kJ/g
Walaiporn Prissanaroon-Ouajai, IC, KMUTNB
Walaiporn Prissanaroon-Ouajai, IC, KMUTNB
 law
If an overall reaction takes place in several steps, its standard
reaction enthalpy ( Hrxn) is the sum of the standard enthalpies of
each step, at the same temperature.
H H Hrxn Hi
A X B
Step1 Step2

Hrxn H H
A B
Walaiporn Prissanaroon-Ouajai, IC, KMUTNB
Key points for Hess law calculation H = H H
H Temperature calculation of H must be done at the same temperature
Scaling up or down with factor n n x H
For reverse reaction H becomes opposite sign.
CH4 g 2O2 g CO2 g 2H2O l : H kJ
2CH4 g 4O2 g 2CO2 g 4H2O l : H 2x( ) kJ
CO2 g 2H2O l CH4 g 2O2 g : H + kJ
In calculation, make sure the steps are (a) balanced (b) in the right direction
and (c) result in the overall reaction.
Walaiporn Prissanaroon-Ouajai, IC, KMUTNB
Calculate the standard enthalpy change ( Ho) of the transition of
C s, graphite) C(s, diamond), given
C(s, graphite) O2 g CO g H1o 393.5 kJ/mol
CO2(g) C(s, diamond) + O2 g H2o +395.4 kJ/mol

H kJ/mol
Walaiporn Prissanaroon-Ouajai, IC, KMUTNB
Calculate H of the reaction : Sn s 2Cl2 g SnCl4 l
Given, Sn s Cl2 g SnCl2 s H1 325 kJ
and SnCl2 s Cl2 g SnCl4 l H2 186 kJ

Walaiporn Prissanaroon-Ouajai, IC, KMUTNB H 511 kJ

Calculate Ho of the reaction 3. Is it endothermic or exothermic
Rxn 1 3H2 g N2 g 2NH3 g H1o -92 4 kJ
Rxn 2 2H2 g O2 g 2H2O g H o2 483 7 kJ
Rxn 3 4NH3 g 3O2 g 2N2 g 6H2O g H o3 ?

Walaiporn Prissanaroon-Ouajai, IC, KMUTNB 1266 3 kJ

Enthalpy change and bond energy

Walaiporn Prissanaroon-Ouajai, IC, KMUTNB

 Bond energy (Bond enthalpy)

Walaiporn Prissanaroon-Ouajai, IC, KMUTNB https://chemju.wordpress.com/2015/07/19/covalent-bond-summary-part-iii/

Calculate enthalpy change H) from bond energy

2H2 g O2 g 2H2O g

Break bonds = absorb energy Form bonds = release energy

Hrxn energy absorbed by reactant energy released from product

Walaiporn Prissanaroon-Ouajai, IC, KMUTNB

 What is the enthalpy change for this reaction and is it endothermic or
exothermic?
Given bond energies: H2 (g) + I2 (g) 2HI (g)
H H = 436 kJ/mol
I I = 151 kJ/mol
H I = 297 kJ/mol

-7 kJ
Walaiporn Prissanaroon-Ouajai, IC, KMUTNB
What is the enthalpy change for this reaction and is it endothermic or
exothermic?
CO2 g 2NH3 g NH -CO-NH + H2O g

125 kJ
Walaiporn Prissanaroon-Ouajai, IC, KMUTNB