Thermochemistry

Module No. 8

1
Energy

 Capacity to do work or to produce heat.

 Law of conservation of energy – energy can
be converted from one form to another but
can be neither created nor destroyed.
 The total energy content of the universe is

constant.

2
Energy

 Potential energy – energy due to position or

composition.
 Kinetic energy – energy due to motion of the
object and depends on the mass of the object
and its velocity.

3
Initial Position

 In the initial position, ball A has a higher

potential energy than ball B.

4
Final Position

 After A has rolled down the hill, the potential energy

lost by A has been converted to random motions of
the components of the hill (frictional heating) and to
the increase in the potential energy of B.

5
Energy

 Heat involves the transfer of energy between

two objects due to a temperature difference.
 Work – force acting over a distance.
 Energy is a state function; work and heat are not
 State Function – property that does not

depend in any way on the system’s past or

future (only depends on present state).

6
Energy
Energy is the capacity to do work
• Radiant 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

6.1
Chemical Energy

 System – part of the universe on which we

wish to focus attention.
 Surroundings – include everything else in the
universe.

8
Energy Changes in Chemical Reaction
Heat is the transfer of thermal energy between two bodies that
are at different temperatures.

Temperature is a measure of the thermal energy.

Temperature = Thermal Energy

400C
900C greater thermal energy

6.2
Thermochemistry
Thermochemistry is the study of heat change in chemical reactions.
The system is the specific part of the universe that is of interest in the study.

open closed isolated

Exchange: mass & energy energy nothing

6.2
Chemical Energy

 Endothermic Reaction:
 Heat flow is into a system.
 Absorb energy from the surroundings.
 Exothermic Reaction:
 Energy flows out of the system.
 Energy gained by the surroundings must be
equal to the energy lost by the system.

11
Chemical Energy
Exothermic process is any process that gives off heat – transfers thermal
energy from the system to the surroundings.

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

H2O (g) H2O (l) + energy

Endothermic process is any 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)

6.2
Concept Check

Is the freezing of water an endothermic or exothermic process? Explain.

Exothermic process because you must remove energy in order to slow the molecules down to form
a solid.

13
Concept Check
Classify each process as exothermic or
endothermic. Explain. The system is
underlined in each example.

a) Your hand gets cold when you touch ice.

b) The ice gets warmer when you touch it.
c) Water boils in a kettle being heated on a
stove.
d) Water vapor condenses on a cold pipe.
e) Ice cream melts.

14
Concept Check
Classify each process as exothermic or
endothermic. Explain. The system is
underlined in each example.

Exo a) Your hand gets cold when you touch ice.

Endo b) The ice gets warmer when you touch it.
Endo c) Water boils in a kettle being heated on a
stove.
Exo d) Water vapor condenses on a cold pipe.
Endo e) Ice cream melts.

15
Concept Check

For each of the following, define a system and

its surroundings and give the direction of energy
transfer.

a) Methane is burning in a Bunsen burner

in a laboratory.
b) Water drops, sitting on your skin after
swimming, evaporate.

16
Concept Check
 For each of the following, define a system and its surroundings and
give the direction of energy transfer.

 Methane is burning in a Bunsen burner in a laboratory.

 System – methane and oxygen to produce carbon dioxide and water;
Surroundings – everything else around it; Direction of energy transfer – energy
transfers from the system to the surroundings (exothermic).

 Methane Water drops, sitting on your skin after swimming,

evaporate.
 System – water drops; Surroundings – everything else around it; Direction of
energy transfer – energy transfers from the surroundings (your body) to the
system (water drops) (endothermic)

17
Thermodynamics
Thermodynamics is the scientific study of the interconversion of heat and
other kinds of energy.
State functions are properties that are determined by the state of the system,
regardless of how that condition was achieved.
energy , pressure, volume, temperature
E = Efinal - Einitial

P = Pfinal - Pinitial

V = Vfinal - Vinitial

T = Tfinal - Tinitial
Potential energy of hiker 1 and hiker 2 is the
same even though they took different paths.

6.3
Thermodynamics

First law of thermodynamics – energy can be converted from

one form to another, but cannot be created or destroyed.

Esystem + Esurroundings = 0

or
Esystem = -Esurroundings

C3H8 + 5O2 3CO2 + 4H2O

Exothermic chemical reaction!

Chemical energy lost by combustion = Energy gained by the surroundings

system surroundings

6.3
Thermodynamics

Another form of the first law for Esystem

E = q + w

E is the change in internal energy of a system

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

6.3
Work

 Work = P × A × Δh = PΔV
 P is pressure.
 A is area.
 Δh is the piston moving

a distance.
 ΔV is the change in

volume.

21
Concept Check

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 V

(a) V = 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) V = 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

6.3
Concept Check
Which of the following performs more work?

a) A gas expanding against a pressure

of 2 atm from 1.0 L to 4.0 L.
b) A gas expanding against a pressure
of 3 atm from 1.0 L to 3.0 L.

They perform the same amount of work.

23
Concept Check
Determine the sign of ΔE for each of
the following with the listed conditions:
a) An endothermic process that performs work.
 |work| > |heat| Δ E = negative
 |work| < |heat| Δ E = positive
b) Work is done on a gas and the process is
exothermic.
 |work| > |heat| Δ E = positive
 |work| < |heat| Δ E = negative

24
Enthalpy and the 1st Law of Thermodynamics
E = q + w

At constant pressure:
q = H and w = -PV

E = H - PV

H = E + PV

6.4
Enthalpy and the 1st Law of Thermodynamics

Enthalpy (H) is used to quantify the heat flow into or out of a system in a
process that occurs at constant pressure.
H = H (products) – H (reactants)

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

Hproducts < Hreactants Hproducts > Hreactants

H < 0 H > 0 6.4

Thermochemical Equations

Is H negative or positive?

System absorbs heat

Endothermic

H > 0

6.01 kJ are absorbed for every 1 mole of ice that melts at 00C and 1
atm.
H2O (s) H2O (l) H = 6.01 kJ

6.4
Thermochemical Equations

Is H negative or positive?

System gives off heat

Exothermic

H < 0

890.4 kJ are released for every 1 mole of methane that is combusted at

250C and 1 atm.

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

6.4
Thermochemical Equations

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

a substance

H2O (s) H2O (l) H = 6.01 kJ

• If you reverse a reaction, the sign of H changes

H2O (l) H2O (s) H = -6.01 kJ

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

change by the same factor n.

2H2O (s) 2H2O (l) H = 2 x 6.01 = 12.0 kJ

6.4
Thermochemical Equations
• The physical states of all reactants and products must be specified in
thermochemical equations.

H2O (s) H2O (l) H = 6.01 kJ

H2O (l) H2O (g) H = 44.0 kJ

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

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

1 mol P4 3013 kJ
266 g P4 x x = 6470 kJ
123.9 g P4 1 mol P4

6.4
A Comparison of H and E

2Na (s) + 2H2O (l) 2NaOH (aq) + H2 (g) H = -367.5 kJ/mol

E = H - PV At 25 0C, 1 mole H2 = 24.5 L at 1 atm

PV = 1 atm x 24.5 L = 2.5 kJ

E = -367.5 kJ/mol – 2.5 kJ/mol = -370.0 kJ/mol

6.4
Heat Capacity and Specific Heat
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 (Cp) 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.

Cp = m x s
Heat (q) absorbed or released:
q = m x s x t

q = Cp x t

t = tfinal - tinitial

6.5
Concept Check
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

t = tfinal – tinitial = 50C – 940C = -890C

q = mst = 869 g x 0.444 J/g • 0C x –890C = -34,000 J

6.5
Constant-Volume Calorimetry

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

No heat enters or leaves! H ~ qrxn

6.5
Constant-Pressure Calorimetry

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!

6.5
6.5