Announcements

If you havent made it to a talk yet for your seminar homework

assignment, then you might be like the following Public Talk.
(A public talk is usually meant to be very accessible.)
Astronomy Public Talk by Dr. Jerey BenneI
PAA A-102, Wednesday April 15, 7:30pm

The exam seaTng chart is posted online. Check out where

your seat is for the Mock Exam (Mon.) and Midterm 1 (Wed.)

Your TAs will be in charge of the Mock Exam and Midterm 1.

AYer class on Friday, Ill rush o to the airport. Ill be giving
seminars at Stanford and Princeton about my own labs
research. Ill be back late Wednesday night. The TAs (and I)
will be checking the Canvas discussion board in the mean Tme.

Lecture 8
Topics
Calorimetry (9.4)
Hesss Law (9.5)

QuesTons well answer

How are temperature and heat related?
How do we measure E and H?
Ho do we determine E or H for
reacTons that we cant study directly?

Constant
Pressure
calorimeter

Constant
Volume
calorimeter

Changes in Enthalpy
Enthalpy

Exothermic
Hinitial

qout

Hfinal

q p = H

If a process is conducted at constant pressure,

all the heat transferred is the enthalpy.
Most chemical and physical processes have an
associated enthalpy change.
CH4(g) + 2 O2(g) CO2(g) + 2 H2O(g)
Hrxn = -802 kJ/mol of rxn

H < 0

Enthalpy

Endothermic
Hfinal

Hinitial
H > 0

qin

2 CO2(g) 2 CO(g) + O2(g) Hrxn = +556 kJ/mol of rxn

What if we double it?
kJ/mol of rxn
4CO2(g) 4CO(g) + 2O2(g) Hrxn = ?+1112
?
H2O(s) H2O(l) Hrxn = +6.02 kJ/mol of rxn
What if we reverse the reacTon?
H2O(l) H2O(s) Hrxn = 6.02
?? kJ/mol of rxn
The
magnitude and sign of the enthalpy in a

thermochemical equa6on is for the process as wri'en!

Gejng to Know q
Add 100 J of energy to
A swimming pool full of water

A beaker full of water

Beaker has fewer

molecules to divide
the 100 J of energy
between.
greater increase
in average
molecular kine6c
energy
greater increase
in T

Which system will experience the

largest increase in temperature?

Gejng to Know q
Add enough heat to the pool and beaker of water to raise
both systems to 40oC.
Pool has more
molecules, so
more energy is
required to
increase its T to
40oC than the
beaker.

Which system has the largest

amount of thermal energy?

Extensive vs. Intensive ProperTes

Extensive physical property: value is proporTonal to the
amount of substance present in the system it describes.

Heat content depends on the number of parTcles available to store

the heattherefore q is an extensive property.
Other extensive proper4es: mass, volume, length, internal energy,
enthalpy

Intensive physical property: value does not depend on the
system size or the amount of substance in the system.

Temperature depends only on the average molecular kineTc energy.

Since dierent-sized collecTons of molecules can have the same
average molecular kineTc energy, T is an intensive property.
Other intensive proper4es: density, pressure, concentraTon, color,
phase (gas, liquid, solid), viscosity, melTng point, boiling point

Constant-Pressure Calorimetry
We can directly measure the enthalpy of a chemical
process if we conduct that process at constant
pressure.

NaOH(aq) + HCl(aq) H2O(l ) + NaCl(aq)

= 58H
kJ/(mol
of reaction)
rxn = ??
By monitoring the change in temperature of the
soluTon during the process, we can determine the
magnitude and sign of the enthalpy.

temp change

q = s m T
experienced by

soluTon
specic heat capacity of mass of the

soluTon, J/g.oC
soluTon

The heat gained/lost by the reacTon is exactly equal to
that lost/gained by the soluTon.

+ qsolution = qrxn

or, qsolution = + qrxn

 5.00 g of ammonium nitrate is dissolved in 500. mL of water at 25.00 oC.

The nal temperature of the soluTon is 23.79 oC. What is the enthalpy
of the dissoluTon process, expressed per mole of ammonium nitrate?
(ssoln = 3.20 J/g.oC, dH2O = 1.00 g/mL)

NH4NO3(s) NH4+(aq) + NO3(aq)

o

Hrxn = ?? J/(mol of reacTon)

TiniTal = 25.00 C
Tnal = 23.79oC
H2O(l)
q
NH4NO3(s)
q
H2O(l)

Heat balance relaTonship:

qsolution = +qrxn

qsolution = ssolution msolution Tsolution

qrxn = nreaction H rxn

qrxn = nNH4 NO3 H rxn

This is what we
want to nd.
For each mole
of reacTon, one
mole of NH4NO3
is consumed.

 5.00 g of ammonium nitrate is dissolved in 500. mL of water at 25.00 oC.

The nal temperature of the soluTon is 23.79 oC. What is the enthalpy
of the dissoluTon process, expressed per mole of ammonium nitrate?
(ssoln = 3.20 J/g.oC, dH2O = 1.00 g/mL)

NH4NO3(s) NH4+(aq) + NO3(aq)

Hrxn = ?? J/(mol of reacTon)

qsolution = ssolution msolution Tsolution

= 3.20 J

1 g
o
500.
mL
+
5.00
g
23.79
C 25.00C

gC
1 mL

= 1955 J
Recall:

qsolution = +qrxn qrxn = +1955 J = nNH4 NO3 H rxn

H rxn =

qrxn
nNH4 NO3

+1955 J
= +31.3 kJ/mol
=
1 mol
5.00 g NH3 NO3

80.05
g

Constant-Volume Calorimetry
Constant-P calorimetry is appropriate for
soluTon-phase reacTons, because the
volume of the system doesnt change.
But what about something like this:
C3H8 ( g ) + 5 O 2 ( g ) 3 CO 2 ( g ) + 4 H 2O(l )

Number of moles of gas change, so

volume would change at constant-P,
making it very dicult to measure the
heat transferred.
What if we hold volume constant?
0 since = PV

E = qV + w

We can nd H by considering the ngas:

H = E + ( PV ) = E + (nRT ) = E + RT ngas

Fixed volume:
w = PV = 0

What is the enthalpy change

associated with changing
graphite into diamond?
Cgraphite Cdiamond Hrxn = ??
This process is dicult to study directly.
But we can readily determine the heats
of combusTon of these two forms of
carbon using constant volume
calorimetry:

C( s ) + O 2 ( g ) CO 2 ( g )

Hesss Law
In going from a par4cular set of reactants to a par4cular set of
products, the overall change in enthalpy is the same whether
the reac4on takes place in one step or in a series of steps.

Cgraphite Cdiamond
C(s, graphite) + O2(g)

CO2(g); Hrxn = -394 kJ/mol

C(s, diamond) + O2(g) CO2(g); Hrxn = -396 kJ/mol

+ CO2(g) C(s, diamond) + O2(g) Hrxn = +396 kJ/mol
C(s, graphite) C(s, diamond) Hrxn = +2 kJ/mol > 0endo
C(s, diamond) C(s, graphite) Hrxn = -2 kJ/mol < 0exo

A Quick Note about Units

Throughout this lecture, Ive tried to be quite careful about heats
of reacTons by pujng a subscript rxn and by showing values
in units of kJ/(mole of reacTon) as in:

N2 (g) + 3H2 (g) 2NH3 (g) Hrxn = -92 kJ/mol of reacTon

However, when you look up heats of reacTons in a table, values
will usually be denoted in simply Joules or kiloJoules, as in:

N2 (g) + 3H2 (g) 2NH3 (g) H = -92 kJ

In other words, when doing problems and
using real data out in the world, you may
need to remind yourself that a heat of
reacTon is for one mole of that reacTon.

A Second Hesss Law Example

Calculate Hrxn for the following reacTon:
H2(g) + Cl2(g) 2HCl(g)

Given the following:

NH3 (g) + HCl (g) NH4Cl(s) Hrxn = -176 kJ/mol of reacTon

N2 (g) + 3H2 (g) 2NH3 (g) Hrxn = -92 kJ/mol of reacTon
N2 (g) + 4H2 (g) + Cl2 (g) 2NH4Cl(s) Hrxn = -629 kJ/mol of reacTon

We need more room.

Lets conTnue this on the next slide.

Find Hrxn for: H2(g) + Cl2(g)

2HCl(g)

Given the following:

NH3 (g) + HCl (g) NH4Cl(s) H = -176 kJ/mol
N2 (g) + 3H2 (g) 2NH3 (g) H = -92 kJ/mol
N2 (g) + 4H2 (g) + Cl2 (g) 2NH4Cl(s) H = -629 kJ/mol

Step 1: Only the rst reacTon contains the product of

interest (HCl). Therefore, reverse the reacTon and mulTply
by 2 to get the stoichiometry correct.

NH3 (g) + HCl (g)

2NH4Cl(s)

NH4Cl(s) Hrxn = -176 kJ/mol

2NH3 (g) + 2HCl (g) Hrxn = 352 kJ/mol

Find Hrxn for: H2(g) + Cl2(g)

2HCl(g)

Given the following:

NH3 (g) + HCl (g) NH4Cl(s) H = -176 kJ/mol
N2 (g) + 3H2 (g) 2NH3 (g) H = -92 kJ/mol
N2 (g) + 4H2 (g) + Cl2 (g) 2NH4Cl(s) H = -629 kJ/mol

Step 2. Need Cl2 as a reactant, therefore, add reacTon 3 to

result from step 1 and see what is leY.

2NH4Cl(s)

2NH3 (g) + 2HCl (g) Hrxn = 352 kJ/mol

N2 (g) + 4H2 (g) + Cl2 (g)

2NH4Cl(s) Hrxn = -629 kJ/mol

N2 (g) + 4H2 (g) + Cl2 (g)

2NH3(g) + 2HCl(g)

Hrxn = -277 kJ/mol

Find Hrxn for: H2(g) + Cl2(g)

2HCl(g)

Given the following:

NH3 (g) + HCl (g) NH4Cl(s) H = -176 kJ/mol
N2 (g) + 3H2 (g) 2NH3 (g) H = -92 kJ/mol
N2 (g) + 4H2 (g) + Cl2 (g) 2NH4Cl(s) H = -629 kJ/mol

Step 3. Use remaining known reacTon in combinaTon

with the result from Step 2 to get nal reacTon.
1

N2 (g) + 4H2 (g) + Cl2 (g)

2NH3(g) + 2HCl(g) Hrxn = -277 kJ/mol

N2 (g) + 3H2(g)
2NH3(g)
Hrxn = -92 kJ/mol


2NH3(g)
3H2 (g) + N2 (g)
Hrxn = +92 kJ/mol



H2(g) + Cl2(g)
2HCl(g)
H = -185 kJ/mol



Need to take the second reaction and reverse it

Another Hess Law Example

Use the informaTon below to determine Hrxn for the reacTon:
3 C(graphite) + 4 H2(g) C3H8(g)

C3H8(g) + 5 O2(g) 3 CO2(g) + 4H2O(l)
H1 = -2219.9 kJ/mol
C (graphite) + O2(g) CO2(g)

H2 = -393.5 kJ/mol
H2(g) + 1/2 O2(g) H2O(l)

H3 = -285.8 kJ/mol

3 CO2(g) + 4H2O(l) C3H8(g) + 5 O2(g)
-H1 = +2219.9 kJ
3 C (graphite) + 3 O2(g) 3 CO2(g)

3(H2) = -1180.5 kJ

4(H3) = -1143.2 kJ
+ 4 H2(g) + 2 O2(g) 4 H2O(l)

3 C(graphite) + 4 H2(g) C3H8(g)

-H1 + 3(H2) + 4(H3)

Hrxn = -103.8 kJ/mol