DEPARTMENT OF PURE AND APPLIED CHEMISTRY

Visayas State University Baybay City, Leyte, Philippines 6521-A

Thermochemistry and
Thermodynamics
 DEPARTMENT OF PURE AND APPLIED CHEMISTRY
Visayas State University Baybay City, Leyte, Philippines 6521-A

Thermodynamics

Scientific study of the interconversion of

heat and other kinds of energy.
 DEPARTMENT OF PURE AND APPLIED CHEMISTRY
Visayas State University Baybay City, Leyte, Philippines 6521-A

Thermochemistry

The study of heat change in chemical

reactions.
 DEPARTMENT OF PURE AND APPLIED CHEMISTRY
Visayas State University Baybay City, Leyte, Philippines 6521-A

System and Surroundings

System – specific part of the universe of

interest. Example: Beaker with NaOH and HCl
Surroundings – the rest of the universe
outside the system.

System + Surroundings = Universe

 DEPARTMENT OF PURE AND APPLIED CHEMISTRY
Visayas State University Baybay City, Leyte, Philippines 6521-A

Types of Systems
Open System – can exchange mass and
energy, usually in the form of heat with its
surroundings.
 DEPARTMENT OF PURE AND APPLIED CHEMISTRY
Visayas State University Baybay City, Leyte, Philippines 6521-A

Types of Systems
Closed System – allows exchange/transfer of
heat or energy but not mass.
 DEPARTMENT OF PURE AND APPLIED CHEMISTRY
Visayas State University Baybay City, Leyte, Philippines 6521-A

Types of Systems
Isolated System – does not allow
exchange/transfer of heat or energy and
mass.
 DEPARTMENT OF PURE AND APPLIED CHEMISTRY
Visayas State University Baybay City, Leyte, Philippines 6521-A

State of the system

Defined by the values of all relevant

macroscopic properties (composition,
energy, temperature, pressure, and
volume.
 DEPARTMENT OF PURE AND APPLIED CHEMISTRY
Visayas State University Baybay City, Leyte, Philippines 6521-A

State Functions

Properties that are determined by the

state of the system regardless of how
that condition was achieved.
Energy, temperature, pressure, and
volume are state functions.
 DEPARTMENT OF PURE AND APPLIED CHEMISTRY
Visayas State University Baybay City, Leyte, Philippines 6521-A

Energy is a State Function

DE = Efinal - Einitial

DP = Pfinal - Pinitial

DV = Vfinal - Vinitial

DT = Tfinal - Tinitial

Potential energy of hiker 1 and hiker 2 is the

same even though they took different paths.
 DEPARTMENT OF PURE AND APPLIED CHEMISTRY
Visayas State University Baybay City, Leyte, Philippines 6521-A

1 Law of Thermodynamics
st

Energy can be converted into one

form or another but cannot be created
or destroyed.

(Based on Law of Conservation of Energy)

 DEPARTMENT OF PURE AND APPLIED CHEMISTRY
Visayas State University Baybay City, Leyte, Philippines 6521-A

1 Law of Thermodynamics
st

Validity of the 1st Law can be tested by

measuring the change in the internal
energy of the system.
ΔEsys = Efinal – Einitial
ΔEsys + ΔEsurr = 0 ; ΔEsys = -ΔEsurr
 DEPARTMENT OF PURE AND APPLIED CHEMISTRY
Visayas State University Baybay City, Leyte, Philippines 6521-A

Heat, Work, and Energy

ΔEsys = q + w

q = heat absorbed / released by the

system
w = work done / by the system
 DEPARTMENT OF PURE AND APPLIED CHEMISTRY
Visayas State University Baybay City, Leyte, Philippines 6521-A

Work (w)

w = - P ΔV

w = positive, work is done on the system

w = negative, work is done by the
system
DEPARTMENT OF PURE AND APPLIED CHEMISTRY
Visayas State University Baybay City, Leyte, Philippines 6521-A
 DEPARTMENT OF PURE AND APPLIED CHEMISTRY
Visayas State University Baybay City, Leyte, Philippines 6521-A

Work

Work is done by the system, Vfinal is larger

than Vinitial
 DEPARTMENT OF PURE AND APPLIED CHEMISTRY
Visayas State University Baybay City, Leyte, Philippines 6521-A

Work

Work is done on the system, Vfinal is smaller

than Vinitial
 DEPARTMENT OF PURE AND APPLIED CHEMISTRY
Visayas State University Baybay City, Leyte, Philippines 6521-A

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?
w = -P DV
(a) DV = 5.4 L – 1.6 L = 3.8 L P = 0 atm

W = -0 atm x 3.8 L = 0 L•atm = 0 joules

(b) DV = 5.4 L – 1.6 L = 3.8 L P = 3.7 atm

w = -3.7 atm x 3.8 L = -14.1 L•atm

101.3 J
w = -14.1 L•atm x = -1430 J
1L•atm
 DEPARTMENT OF PURE AND APPLIED CHEMISTRY
Visayas State University Baybay City, Leyte, Philippines 6521-A

Heat (q)

The transfer of thermal energy between

two bodies that are at different
temperatures.
q = positive, heat is added on the system
q = negative, heat released by the
system
DEPARTMENT OF PURE AND APPLIED CHEMISTRY
Visayas State University Baybay City, Leyte, Philippines 6521-A
 DEPARTMENT OF PURE AND APPLIED CHEMISTRY
Visayas State University Baybay City, Leyte, Philippines 6521-A

Endothermic and Exothermic

Endothermic process = heat supplied to

the system by the surroundings

Exothermic process = heat given off by

the system to the surroundings
 DEPARTMENT OF PURE AND APPLIED CHEMISTRY
Visayas State University Baybay City, Leyte, Philippines 6521-A

Endothermic and Exothermic

 DEPARTMENT OF PURE AND APPLIED CHEMISTRY
Visayas State University Baybay City, Leyte, Philippines 6521-A

Endothermic and Exothermic

Exothermic process
2H2 (g) + O2 (g) 2H2O (l) + energy

H2O (g) H2O (l) + energy

Endothermic process

energy + 2HgO (s) 2Hg (l) + O2 (g)

energy + H2O (s) H2O (l)

DEPARTMENT OF PURE AND APPLIED CHEMISTRY
Visayas State University Baybay City, Leyte, Philippines 6521-A
DEPARTMENT OF PURE AND APPLIED CHEMISTRY
Visayas State University Baybay City, Leyte, Philippines 6521-A
 DEPARTMENT OF PURE AND APPLIED CHEMISTRY
Visayas State University Baybay City, Leyte, Philippines 6521-A

Endothermic
 DEPARTMENT OF PURE AND APPLIED CHEMISTRY
Visayas State University Baybay City, Leyte, Philippines 6521-A

Exothermic
DEPARTMENT OF PURE AND APPLIED CHEMISTRY
Visayas State University Baybay City, Leyte, Philippines 6521-A
DEPARTMENT OF PURE AND APPLIED CHEMISTRY
Visayas State University Baybay City, Leyte, Philippines 6521-A
DEPARTMENT OF PURE AND APPLIED CHEMISTRY
Visayas State University Baybay City, Leyte, Philippines 6521-A
 DEPARTMENT OF PURE AND APPLIED CHEMISTRY
Visayas State University Baybay City, Leyte, Philippines 6521-A

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

thermochemical equations.

H2O (s) H2O (l) DH = 6.01 kJ

H2O (l) H2O (g) DH = 44.0 kJ

How much heat is evolved when 266 g of white phosphorus (P4) burn in air?

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

1 mol P4 3013 kJ
266 g P4 x x = 6470 kJ
123.9 g P4 1 mol P4
The specific heat (s) of a substance is the amount of heat (q) required to raise the
DEPARTMENT OF PURE AND APPLIED CHEMISTRY
temperature of one gram of the substance by one degree Celsius.
Visayas State University Baybay City, Leyte, Philippines 6521-A

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

Heat (q) absorbed or released:

q = m x s x Dt

q = C x Dt

Dt = tfinal - tinitial
 DEPARTMENT OF PURE AND APPLIED CHEMISTRY
Visayas State University Baybay City, Leyte, Philippines 6521-A

How much heat is given off when an 869 g iron bar cools from 94 0C to 50C?

s of Fe = 0.444 J/g • 0C

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

q = msDt = 869 g x 0.444 J/g • 0C x –89

= 0-34,000
C J
 DEPARTMENT OF PURE AND APPLIED CHEMISTRY
Visayas State University Baybay City, Leyte, Philippines 6521-A

Thermochemistry
DEPARTMENT OF PURE AND APPLIED CHEMISTRY
Visayas State University Baybay City, Leyte, Philippines 6521-A
DEPARTMENT OF PURE AND APPLIED CHEMISTRY
Visayas State University Baybay City, Leyte, Philippines 6521-A
DEPARTMENT OF PURE AND APPLIED CHEMISTRY
Visayas State University Baybay City, Leyte, Philippines 6521-A
DEPARTMENT OF PURE AND APPLIED CHEMISTRY
Visayas State University Baybay City, Leyte, Philippines 6521-A
DEPARTMENT OF PURE AND APPLIED CHEMISTRY
Visayas State University Baybay City, Leyte, Philippines 6521-A
DEPARTMENT OF PURE AND APPLIED CHEMISTRY
Visayas State University Baybay City, Leyte, Philippines 6521-A
DEPARTMENT OF PURE AND APPLIED CHEMISTRY
Visayas State University Baybay City, Leyte, Philippines 6521-A
DEPARTMENT OF PURE AND APPLIED CHEMISTRY
Visayas State University Baybay City, Leyte, Philippines 6521-A
DEPARTMENT OF PURE AND APPLIED CHEMISTRY
Visayas State University Baybay City, Leyte, Philippines 6521-A
DEPARTMENT OF PURE AND APPLIED CHEMISTRY
Visayas State University Baybay City, Leyte, Philippines 6521-A
 DEPARTMENT OF PURE AND APPLIED CHEMISTRY
Visayas State University Baybay City, Leyte, Philippines 6521-A

Chemistry in Action: Bombardier Beetle Defense

C6H4(OH)2 (aq) + H2O2 (aq) C6H4O2 (aq) + 2H2O (l) DH0 = ?

C6H4(OH)2 (aq) C6H4O2 (aq) + H2 (g) DH0 = 177 kJ/mol

H2O2 (aq) H2O (l) + ½O2 (g) DH0 = -94.6 kJ/mol

H2 (g) + ½ O2 (g) H2O (l) DH0 = -286 kJ/mol

DH0 = 177 - 94.6 – 286 = -204 kJ/mol

Exothermic!
DEPARTMENT OF PURE AND APPLIED CHEMISTRY
Visayas State University Baybay City, Leyte, Philippines 6521-A
DEPARTMENT OF PURE AND APPLIED CHEMISTRY
Visayas State University Baybay City, Leyte, Philippines 6521-A
DEPARTMENT OF PURE AND APPLIED CHEMISTRY
Visayas State University Baybay City, Leyte, Philippines 6521-A
DEPARTMENT OF PURE AND APPLIED CHEMISTRY
Visayas State University Baybay City, Leyte, Philippines 6521-A
DEPARTMENT OF PURE AND APPLIED CHEMISTRY
Visayas State University Baybay City, Leyte, Philippines 6521-A
DEPARTMENT OF PURE AND APPLIED CHEMISTRY
Visayas State University Baybay City, Leyte, Philippines 6521-A
DEPARTMENT OF PURE AND APPLIED CHEMISTRY
Visayas State University Baybay City, Leyte, Philippines 6521-A
DEPARTMENT OF PURE AND APPLIED CHEMISTRY
Visayas State University Baybay City, Leyte, Philippines 6521-A
 DEPARTMENT OF PURE AND APPLIED CHEMISTRY
Visayas State University Baybay City, Leyte, Philippines 6521-A

How does the entropy of a system change for each of the following processes?

(a) Condensing water vapor

Randomness decreases Entropy decreases (DS < 0)

(b) Forming sucrose crystals from a supersaturated solution

Randomness decreases Entropy decreases (DS < 0)

(c) Heating hydrogen gas from 600C to 800C

Randomness increases Entropy increases (DS > 0)

(d) Subliming dry ice

Randomness increases Entropy increases (DS > 0)

DEPARTMENT OF PURE AND APPLIED CHEMISTRY
Visayas State University Baybay City, Leyte, Philippines 6521-A
DEPARTMENT OF PURE AND APPLIED CHEMISTRY
Visayas State University Baybay City, Leyte, Philippines 6521-A
DEPARTMENT OF PURE AND APPLIED CHEMISTRY
Visayas State University Baybay City, Leyte, Philippines 6521-A
DEPARTMENT OF PURE AND APPLIED CHEMISTRY
Visayas State University Baybay City, Leyte, Philippines 6521-A
 DEPARTMENT OF PURE AND APPLIED CHEMISTRY
Visayas State University Baybay City, Leyte, Philippines 6521-A

Entropy Changes in the Surroundings (DSsurr)

Exothermic Process Endothermic Process

DSsurr > 0 DSsurr < 0
 DEPARTMENT OF PURE AND APPLIED CHEMISTRY
Visayas State University Baybay City, Leyte, Philippines 6521-A

Third Law of Thermodynamics

The entropy of a perfect crystalline substance is zero at the absolute
zero of temperature.
DEPARTMENT OF PURE AND APPLIED CHEMISTRY
Visayas State University Baybay City, Leyte, Philippines 6521-A
DEPARTMENT OF PURE AND APPLIED CHEMISTRY
Visayas State University Baybay City, Leyte, Philippines 6521-A
DEPARTMENT OF PURE AND APPLIED CHEMISTRY
Visayas State University Baybay City, Leyte, Philippines 6521-A
DEPARTMENT OF PURE AND APPLIED CHEMISTRY
Visayas State University Baybay City, Leyte, Philippines 6521-A

DG = DH - TDS