Chemistry 5

Chapter-7
Thermochemistry
Part-2

21 October 2002

Great Job on Exam!

 Heat & Work
ƒ Three ways to increase energy of system?
• adding material to it
• heating it
• doing work on it
-- for example, winding up a spring or pushing
a weight.
-- it takes energy to do work

ƒ Work = force x distance

Consider expansion of gas– how much work is done?

ƒ Demonstration- Observations?

• If pressure inside can exceeds external pressure, then

lid flys off!
• How much work is done???
 WORK
ƒ Pressure-Volume Work:

ƒ Work (w) = force (F) x distance (h)

(remember: P = F/A)
= PxAxh
= P x ∆V

ƒ w = - Pext x ∆V
• significance of negative sign?
When gas expands (∆V > 0), work is done on surroundings; the
negative sign signifies energy leaves (as work) the system.
• significance of Pext?
External pressure against which system expands or that
compressing the system.

ƒ Units The pressure-volume work (L-atm) can be expressed

in more familiar energy units of joule (J) using ideal
gas constants: 101.33 J/L-atm
 Energy, Heat & Work
ƒ Internal Energy, U
• Is the total kinetic + potential
energy of the system

• Includes energy associated

with molecular motions:

• A system only contains

internal energy; it does not
contain energy in the form of
heat or work.

ƒ Changing the internal energy

• The internal energy of a system can be
changed by heating or doing work.
• cold water Æ hot water

Ucold heat Uhot

∆U = Uhot – Ucold, change in internal energy

= Ufinal - Uinitial
Changing the Internal Energy

final state, Uf
INTERNAL ENERGY, U

work, w
∆U = Uf – Ui = q + w

heat, q

initial state, Ui

ƒ Change in internal energy is the sum of the

energy transferred as heat and that
transferred as work.
ƒ Heat and work are equivalent ways of
changing the energy of a system.
 First Law of Thermodynamics
ƒ First Law
• isolated system
The internal energy of an isolated system is
constant: ∆Uisolated sys = 0
• system not isolated
For a system that is not isolated: ∆U = q + w

ƒ Some conventions:
• energy entering system
Energy entering the system has positive sign:
heat absorbed by system, q > 0
work done on system, w > 0

• energy leaving system

Energy leaving the system has
negative sign:
heat released by system, q < 0
work done by system, w < 0
 Changing Internal Energy

∆U = q + w
C8H18(l) + (25/2) O2(g)
ENERGY

Uinitial

8 CO2(g) + 9H2O(g) E lost as

E lost as HEAT
HEAT and WORK
Ufinal

Extract all the energy change as heat

Extract energy as work and heat (a car)
 Changing Internal Energy

∆U = q + w
ENERGY

Initial State

q<0 q<0
w=0 w<0

Final State

We can have different combinations of q and w, to

reach same final state.
∆U depends only on initial and final states!
 State Functions
ƒ What is a state function
• A state function is a property with a value that
depends only on the current state of system and
not how it was prepared.
• Key to thermochemistry is that the change in a
state function is independent about how change
occurred; that is, independent of pathway.
ƒ Internal energy is a state function
• It is difficult to obtain an absolute value of U;
however, it is generally the change in internal
energy, ∆U, that is most important.
ƒ Path Dependent Functions
• heat & work values depend on the path followed
when a system undergoes change!

• Example– consider expansion of ideal gas one

vs. two steps.
 Heats of Reaction– Enthalpy
ƒ Constant Volume
• ∆U = q + w
= q – Pext∆V
=q–0
= qV

ƒ Constant Pressure
• importance?
Many (most) chemical and biochemical reactions
are carried out under constant pressure (not
constant volume); qV ≠ qP
• Enthalpy Change, ∆H
At constant pressure:
∆U = qP + w
= qP - P∆V
qP = ∆U + P∆V

Since U, P & V are all state functions, qP is also one.

We give this a special name– enthalpy, H!
∆H = ∆U + P∆V
Enthalpy vs. Internal Energy Changes
ƒ ∆U = ∆H – P∆V; how important is work term?

2CO(g) + O2(g) Æ 2CO2(g)

qP = -566 kJ = ∆H

Evaluate P-V work: P∆V = P(Vf – Vi)

=RT(nf – ni)

∆U = ∆H – P∆V, constant pressure

= -564 kJ
 Enthalpy: Other Key Points
ƒ Changes of State
• vaporization
Compound (l) Æ Compound (g), ∆Hvap > 0

• melting
Compound (s) Æ Compound (l), DHmelt > 0
• sublimation
Compound (s) Æ Compound (g), DHsub > 0

ƒ Standard States
Enthalpy changes are precisely defined with respect
to state. We can define standard state enthaply,
∆Ho,which corresponds to change for reactants and
products in standard state.
Temperature usually specified as 298.15 K.
ƒ Endothermic & Exothermic Processes

Endothermic– heat goes

into system during
reaction.
Exothermic– hear released
by system during reaction.