Lecture 2: Enthalpy

Reading: Zumdahl 9.2, 9.3

Outline
Definition of Enthalpy (H)
Definition of Molar Heat Capacity (Cv and Cp)
Calculating using Cv and Cp
Changes in E and H as well as q and w for different
paths
Problems: Z9.11,Z9.23-25(no calculations required),
Z9.27, Z9.29

Definition of Enthalpy
Thermodynamic Definition of Enthalpy (H):
H = E + PV
E = energy of the system
P = pressure of the system
V = volume of the system
Each quantity can be determined by measuring the system, so
they are quantities that depend on the state of the system.
What does depend on the state of the system mean?
Can determine change (eg DE) by looking at system before and
after, not during the change
This is not true of q and w, you must know how the system
changes (during the change) to determine q and w.
State function depend on the state of the system defined by P,V
and T for a gas.

Definition of Enthalpy (cont.)

Consider a process carried out at constant pressure.
(Such as all the reactions in our body and in the
laboratory, usually.)
If work is of the form -PV, then:

E = q + w = q P V

qp is heat transferred at constant pressure.

( isobaric ) then q p q
H = E + ( PV ) = qP PV + PV = qP
If: P = 0

H = qP

Therefore, for reactions run at constant pressure the heat

energy that flows (in or out), which can be measured, is
equal to the reaction enthalpy, which is a state function.
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Changes in Enthalpy
Consider the following expression for a chemical reaction:
H = Hproducts - Hreactants
If H >0, then qp >0. The reaction is endothermic
If H <0, then qp <0. The reaction is exothermic
Endo- means into; exo- means out from.

Enthalpy Changes: Pictorially

Entha lpy

Similar to previous discussion

for Energy.
Hinitial
q out
Hfinal
H < 0

Heat comes out of system,

enthalpy decreases (ex. Cooling
water).

Entha lpy

Heat goes in, enthalpy increases

(ex. Heating water)
Hfinal

Hinitial
H > 0

q in

Is it possible to have a reaction

go that takes heat (I.e. gets
cold)?
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Heat Capacity: The relation of internal energy to temperature

Recall from Chapter 5 (section 5.6):

(KE)average = 3/2RT (ideal monatomic gas)

Temperature is a measure of molecular motion.
E = 23 PV = 23 nRT
Then for a change in temperature, the energy change is:
E = n ( 23 R ) T
In thermodynamic terms, an increase in system temperature
corresponds to an increase in system kinetic energy ( i.e., T
is proportional to E), and DE depends only the the
temperature change (and nothing else).
This relation is distinct from the first law and
complementary to it. Both forms of DE hold.
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Qualitative Problems we can answer (Z9.22-26)

DE depends only on DT, what about DH?
H = E + ( PV ) = E + ( nRT )

H = n ( 23 R ) T + nRT = n ( 23 R + R ) T
So yes, DH depends only on DT as well. The
proportionality is larger (add nR)
Therefore both E and H are state functions (unlike q and
w). Because: If you know the temperature before and
after the change, the amount of heat and work flow do
not matter and changes in P and V alone do not matter.
If a reaction is exothermic, what precautions do you
need to make when it happens? [Hint: Cool it.]
For the formation of (2 moles of) NO (from air)
DH=180kJ. What does this imply about it happening?
Why high temperatures?
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How Energy and Enthalpy connect to reactions

Z9.25. Have the reaction to form water:

2 H 2 ( g ) + O2 ( g ) R 2 H 2O ( A )

H = 572kJ

How much heat do you get if you form 1 mole of water?

How about how much heat if you make 1.8 grams of water? [Hint
convert grams to moles and scale the heat proportionally.]
What is the heat for the reaction to make the two gasses from water?
[Whatever you do to the reaction, do it to the energy/enthalpy for the
reaction. In this case change direction, which is change DH sign.]
How much heat did the Hindenberg give off when it burned? [Hint:
Convert volume to number of moles. The above reaction tells you the
heat per mole of H2 burned is 286kJ.

Heat Capacity at Constant V (isochoric)

V = 0

How much energy (at constant volume) in the form of heat

is required to change the gas temperature by an amount T?

E = qV PV = qV = n ( 23 R ) T
qV
= ( 23 R )
CV
n T

No PdV work was allowed. See Table 9.1

The heat capacity, Cv = 3/2 R ,is the amount of heat
required to raise the temperature by one degree (of one
mole of a monoatomic ideal gas at constant volume). Cv is
referred to as the constant volume (molar) heat capacity.
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Heat Capacity at Constant P

What about at constant pressure? In this case, PdV type work

also occurs:
The change in enthalpy with temperature is known, and the
heat released at constant pressure in the enthalpy.
Therefore we can define a heat capacity at constant
pressure as:
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qP = H = n ( 2 R + R ) T

qP
= ( 23 R + R ) = CV + R
CP
nT

Physically Cp is greater than Cv: When warming an ideal

gas the heat goes into increasing the energy in the 3
translational modes. Now at constant pressure the heat is
also used to expand the cylinder and do productive work on
the surroundings (work is negative). So the gas can
absorbs more heat (under constant P conditions) for the
same temperature rise (than under constant V conditions).10

Cv for Monatomic Gases

E = 12 mv 2 = 32 nRT

What are the energetic

degrees of freedom for
a monatomic gas?
x

Ans: Just translations,

which contribute 3/2R
to Cv.

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Cv for Polyatomics
What are the energetic
degrees of freedom for a
polyatomic gas?

Iz
Iy

N2 C v = 5/2 R (approx.)

Iz

Iy
Ix

Ans: translations, rotations,

and vibrations. All of
which may contribute to
Cv (depends on T).

NO2 C v = 7/2 R (approx.)

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Variation in Cp and Cv
3
2

R = 12.47 J

mole K

Cv

Cp

Ar, He, Ne

12.47

20.8

H2

20.54

28.86

CO2

Units: J/mol.

28.95

37.27

Monatomics:
Cv = 3/2 R
Cp = 5/2 R

Polyatomics:
Cv > 3/2 R
Cp > 5/2 R
But.Cp = Cv + R

The idea is called the equipartition of energy which means that

each possible way of moving (mode) gets about R for the
molar heat capacity. (See Table 9.1).
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Keeping Track: Table 9.2 of Text is great.

See also Table 9.1 for real numbers R~8.3J/Kmol

Ideal Monatomic Gas (IMG)

Cv = 3/2R
Cp = Cv + R = 5/2 R
Polyatomic Gas
Cv > 3/2R
Cp > 5/2 R
The heat capacity will be a given
quantity or you are told it is an
IMG.

All Ideal Gases (IG)

(regardless of process)

E = nCvT
H = nCpT
Cp = Cv + R
Notice: For the same
process the enthalpy
change is larger than the
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energy change.

Example (A part of Z9.29)

What is q, w, E and H for a process in which one mole
of an ideal monatomic gas with an initial volume of 15
liters and pressure of 3.0 atm is heated until a volume of 55
liters is reached with pressure unchanged?
A gas is expanding by heating. What are the signs of the
different terms?
Pinit = 3 atm

Pfinal = 3 atm

Vinit = 15 l

Vfinal = 55 l

Tinit = ? K
Tfinal = ? K
Before you start; realize you may not need the initial and final
temperature separately; only the difference. The process is a
DP=0 process. DE and DH are determined only by DT. It is a
IMG, so you know the two heat capacities. On a test the first
thing you write down is DE and DH in terms of DT, which you
then need to find. Then ask, can I determine the work, and
finally you find the heat by rearranging the first law.

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Problem Z9.29
R=8.31451 J/(mol-K) = 0.08206 (liter-atm)/(mol-K)
Adapt PV=nRT to the change for the process:
PDV =nRDT Now we can determine DT.
V = ( 55 15) A = 40A
T =

( 3atm )( 40l )

(1mol ) .0821 l.atm

mol. K

= 1460 K

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Example (cont.)
From the temperature change, and IMG, 1 mole, get change in energy
and enthalpy; and the definition of PdV work and the first law give
the work and heat for this process.

E = nCv T = (1mol ) 12.5 J

1460 K ) = 18.2kJ
(
mol.K
5
H = nC p T = E = 30.kJ
3
w = Pext V = ( 3atm )( 40l ) 101.3 J
= 12kJ
l.atm

q = E w = 18 ( 12 ) = 30 J
It is no coincidence that q and DH are the same: This is a
constant pressure process for which q=qp=DH.
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Problem Z9.29 Two Paths

We have done step one (from A to C) of the PV diagram.
The goal is to go from A to B by two different paths. The first (blue)
path takes you through C and the second (red) path through D.
Need to compute DE, DH, w and q for each step.
The goal is to realize that DE and DH when we sum steps 1 and 2 will
give the same result as when we sum steps 3 and 4. They are path
independent.
w and q will be different for
the two different paths.
Notice that the work on the
path through D must be larger
than the work on the path
through C because the DV is
the same but the pressure is
higher. There is no work in
either steps 2 or 3 as DV=0.
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The second step in A-C-B path

We have done an isobaric process; so what is
different for an isochoric process?
I.G. difference equation is a bit different

VP=nRT Solve for T.

There is no work: w=0;
E and H are computed the same way, based
on the temperature change.
It is a constant volume change so q=qV=E

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