l12 Chapt7-2 Web
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Trip AdlerChemistry 5
Chapter-7
Thermochemistry
Part-2
21 October 2002
Great Job on Exam!
Heat & Work
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
Work = force x distance
Consider expansion of gas– how much work is done?
Demonstration- Observations?
• If pressure inside can exceeds external pressure, then
lid flys off!
• How much work is done???
WORK
Pressure-Volume Work:
Work (w) = force (F) x distance (h)
(remember: P = F/A)
= PxAxh
= P x ∆V
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.
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
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.
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
Change in internal energy is the sum of the
energy transferred as heat and that
transferred as work.
Heat and work are equivalent ways of
changing the energy of a system.
First Law of Thermodynamics
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
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
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.
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.
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
Constant Volume
• ∆U = q + w
= q – Pext∆V
=q–0
= qV
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
∆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
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
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.
Endothermic & Exothermic Processes
Endothermic– heat goes
into system during
reaction.
Exothermic– hear released
by system during reaction.
