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Thermochemistr

y
Energy Changes In Chemical Reactions
Learning Catalytics:

Chapter 6
Coverage:
6.2 The Nature of Energy: Key Definitions
6.3 The First Law of Thermodynamics: There is No Free Lunch
6.4 Quantifying Heat and Work
6.5 Measuring U for Chemical Reactions: Constant-Volume Calorimetry
6.6 Enthalpy: The Heat Evolved in a Chemical Reaction at Constant

Pressure
6.7 Constant-Pressure Calorimetry: Measuring rH
6.8 Relationships involving rH
6.9 Determining Enthalpies of Reaction from Standard Enthalpies of
Formation

Omitted
6.1 Chemical Hand Warmers
6.10 Energy Use and the Environment
2

Energy basics
Internal energy, heat, work and all that

Terminology
Thermochemistry: Study of changes in

energy functions that accompany chemical


reactions
E.g. 4 Fe(s) + 3 O2(g) 2 Fe2O3(s) rH =

-1648.4 kJ/mol

System: Part of the universe under study


E.g. Known masses of Fe(s) and O2(g) in a
vessel
Surroundings: Everything else

System + Surroundings = Universe


4

Energy from a chemists


POV
Energy:
Capacity of chemical system to do work or
transfer heat
Kinetic energy:
Energy of a system due to the motion of its
particles
A.k.a. thermal energy
Potential energy:
Energy a system possesses due to the positions
of the particles in a field
E.g. molecules in a gas vs same molecules in a
5
liquid

Units of Energy
SI: joule, J (nJ, J, mJ, kJ, MJ, GJ,)
Small j for joule, capital for symbol
Important: case of prefix matters (m = 10-3, M
= 106)
No period after symbol
Other units in common usage:
Calorie (cal) = 4.184 J
Big calorie (Cal) = 4,184 J (a kilocalorie, or
kcal)
Kilowatt-hour (kWh)

1000 W for one hour = 1000 (J/s) 3600 s = 3.6 MJ


6

Questions
Does water at 20C possess energy? Explain.
What measurable value contains information

about the kinetic energy of a chemical system?


Which has higher energy: liquid water at 100C or
steam at 100C? Explain.

Energy
Internal energy (U): sum of energy of all

particles in system (kinetic + potential)


Heat (q): energy exchanged with
surroundings by atomic-scale collisions, due to
a temperature difference
Work (w): energy exchanged with
surroundings by macroscopic motion of
surroundings
Heat and work are mechanisms by which
energy is exchanged between system and
surroundings

Questions
Which system has more energy, a litre of

water at 100C or a swimming pool at 20C?


Which can transfer more heat (to, say, melt

ice)?

A litre of water at 20C is put into contact with

a litre of water at 10C. Which way will heat


flow?
Heat flows from high temp to low (compare

diffusion)

Does a litre of water at 20C possess more

heat than a litre of water at 10C?


9
No: Systems do not possess heat, they transfer

Heat/Work Analogy
Does your bank account contain the cash and

cheques you deposited?


Cash & cheques are mechanisms for

transferring value
BUT: Bank accounts do not contain cash or
cheques
What does a bank account contain? A balance.

Does a chemical system contain heat and

work?
Heat & work are mechanisms for moving

energy
BUT: Chemical systems do not contain heat10or

Sign Convention for q


and w
Energy entering the system is positive
Heat absorbed by or work done on the system
Energy leaving the system is negative
Heat released from or work done by system
U = q + w < 0 means more energy left the

system than entered it during a change


U = q + w > 0 means more energy entered
the system than left it during the change

11

Heat/Work Analogy
When money enters your bank account (by

cheques or cash) your account balance (B)


increases
B > 0

When money leaves your bank account (by

cheques or cash) your account balance (B)


decreases
B < 0

12

Temperature question
The temperature of a system decreases

during a thermodynamic change. Does that


mean that the system lost heat to the
surroundings?
No
What does temperature measure?
Kinetic internal energy (thermal energy)
A T decrease means the system lost internal

energy
It might have lost energy as heat or as work
13

LC: Sign Convention


During a reaction, some of the energy released
by the system is used to move a mass up a hill,
while the air temperature of the surroundings
near the system increases by 50 K. What are
the relative values for q, w and U,
respectively?
q
B. q
C. q
D. q
A.

>
>
<
<

0
0
0
0

;
;
;
;

w
w
w
w

>
<
>
<

0
0
0
0

;
;
;
;

U
U
U
U

>
=
=
<

0
0
0
0
14

Solution
During a reaction, some of the energy released by the
system is used to move a mass up a hill, while the air
temperature of the surroundings near the system
increases by 50 K. What are the relative values for q, w
and U, respectively?
ANS = D
Is w positive, negative, or zero?

NEGATIVE: work done by system to raise the mass


Is q positive, negative, or zero?
NEGATIVE: heat released raises T of surroundings
Is U positive, negative, or zero?
NEGATIVE: q and w are both < 0
15

LC: Sign Convention


A gas is contained in a piston-andcylinder system, oriented vertically. On
top of the cylinder there is a mass. When
the gas is heated it expands, and the
mass is lifted. The energy used to lift the
mass is exactly the same as the energy
absorbed from the heater. What are the
signs for q, w and U, respectively?
A. q = +; w = + ; U = +
B. q = +; w = - ; U = 0
C. q = -; w = + ; U = 0
D. q = -; w = - ; U = 16

Solution
A gas is contained in a piston-and-cylinder system,
oriented vertically. On top of the cylinder there is a
mass. When the gas is heated it expands, and the mass
is lifted. The energy used to lift the mass is exactly the
same as the energy absorbed from the heater. What are
the signs for q, w and U, respectively? ANS = B
Is q > 0, < 0, or = 0?

ANS: q > 0. gas is heated


Is w > 0, < 0, or = 0?
ANS: w < 0. Work done by system to lift mass
Is U > 0, < 0, or =0?
ANS: U = q + w = 0. Work (-) and heat (+) balance
17

State functions
and path functions

18

State & State Function


Thermodynamic state
defined by specifying the TD variables; e.g. T, P,
, composition
Thermodynamic state function
TD quantity of the system
Depends solely on the TD state
U is a state function
Change in a state function (e.g. U) does not

depend on the mechanism to go from one state


to the other
19

Analogy: Altitude on a Mountain

20

LC: State Functions


Sample A: 50 g of H2O (g) at 400 K and 1 atm is compressed
until it condenses, then the liquid is cooled to 300 K. Pressure is
reduced to 1 atm while the temperature is maintained at 300 K
Sample B: 50 g of H2O (s) at 200 K and 1 atm is heated to the
melting point, and then the liquid water is further heated to 300
K under 1 atm pressure
Which water sample has the higher internal energy in the
final state?
A. Sample A
B. Sample B
C. Neither
21

Solution
Answer is C
Internal energy (U) is a state function
State functions have one value per state of the
system
Final state of A is same as final state of B
Therefore, A and B have same internal energy

22

What isnt a state


function?
Heat (q) and work (w) are not state functions
In going from state i (initial) to state f (final),
U must change by
U = Uf - Ui = q + w
Infinite pairs of q + w that add to U
q and w called path functions (depend on

path)
BUT: Uf and Ui do not depend on the path
23

Heat and heat transfer


Measuring and calculating heat exchange between
bodies

24

Specific Heat Capacity


100
J
hea
t

10 g
water
25.00 C

100
J
hea
t

10 g Cu
25.00 C

10 g
water
27.39 C

=4.18Jg1C1

10 g Cu
50.97 C

Cs=0.385Jg1C1
25

Specific Heat Capacity


Values are specific to substance or mixture
4.184 is for water, nothing else!
Available in tables (e.g. Table 6.4) for pure

substances
Allow calculation of temperature changes
E.g. How much heat is required to raise the

temperature of a glass of water (250 g) from


20C to 100C
ANS: q = mCsT
= (250 g)(4.184 J/g/C)(100 20)C
= 83.7 kJ
26

Heat exchange
Heat entering the system is equal and

opposite heat leaving the surroundings


q = -qsurr
mCsT = - msurrCs,surrTsurr
E.g. A block (25 g) of copper (the system) at
100C is submerged in 100 g of water (the
surroundings) at 20C. What is the final
temperature of the water when equilibrium is
reached?
Cs,H2O = 4.184 J/g/C; Cs,Cu = 0.385 J/g/C
27

Heat exchange

28

Notes on specific heat


capacity
1C change in temp = 1 K change in temp
BUT: temp in K temp in C!
Molar heat capacity
For pure substances only
E.g. for water
(4.184 J/g/C)(18.0 g/mol) = 75.38 J/mol/C
More generally: Cm = CsM

29

Pressure-Volume Work

30

Pressure-Volume Work
FinalState

InitialState

Pext

Pext

Vi
Pi>Pext

Gasexpands
againstPextuntil
pressuresequalise
Workdone:
w=Pext(VfVi)

Vf
Pf=Pext
31

Pressure-Volume Work
w = Fd
F is the force due to the external pressure
d is the distance the piston travels

w = (PextA)d
A is the cross-sectional area of the piston

w = Pext(Ad) = PextV
Sign convention: gas does work on surroundings when

it expands; therefore

w = -PextV
If Pext and P are in equilibrium during change
w = -P V
32

PV work example
11.7 L of gas in a cylinder-and-piston system

is initially at equilibrium with its surroundings


(Pext = 1.03 bar).
Heat is added slowly and the gas expands in

equilibrium with the surroundings until the


piston reaches the end of the cylinder and
stops.
Heat continues to be added while the piston is
stopped.
The final volume of the gas is 24.1 L and the
total heat added is 1500 J.
33

PV work example
Work: System and surroundings are in equilibrium so

w = -P V

Remember to change units: L to m 3 and bar to

Pa
w = - (1.03105 Pa)(24.1 11.7)10-3 m3 = - 1.28103
J
Heat is +1500 J so

U = q + w = 1500 J 1280 J = +220 J


34

Constant-Volume
Calorimetry
Measuring heats of reaction

35

Calorimetry
Purpose: measure

heat of combustion
V = 0 so w = 0

Process:
Burn substance
completely in
bomb
Carefully monitor
T of calorimeter
Calculate heat
transferred
36

Heat Capacity
First step: determine heat capacity of

calorimeter
Ccal = qcal/Tcal
Burn substance that gives off known amt of

heat

Once Ccal is known, can use bomb calorimeter

to measure heats of other combustion


reactions
Heat of reaction (qr) equal and opposite to heat

gained by calorimeter

qr = -qcal = - Ccal Tcal

37

Note on constant V
reactions
The energy change associated with a reaction

is denoted
rU
Since w = 0 when V = 0,
rU = q + w = qr,v
where the subscript v denotes constant volume

38

LC: Calorimetry
When 1.730 g of benzoic acid is burned in
oxygen in a calorimeter, the temperature of the
calorimeter increases by 2.95 K. If the heat
released from combustion of 1.000 g of benzoic
acid is 26.38 kJ, what is the heat capacity of the
calorimeter?
A. 13.0 kJ/K
B. 45.64 kJ/K
C. 15.5 kJ/K
D. 135 kJ/K
39

Answer
C. 15.5 kJ/K
Heat absorbed by the calorimeter is
qcal = (1.730 g)(26.38 kJ/g) = 45.64 kJ
And Tcal = 2.95 K
Ccal = qcal/Tcal
= (45.64 kJ)/(2.95 K)
= 15.5 kJ/K
15.5 kJ of heat required to raise temp by 1 K

40

LC: Calorimetry
A calorimeter (Ccal = 13.0 kJ/K) is used to measure
the energy of reaction for combustion of a
substance with molar mass 205.9 g/mol.
When 1.151 g of the substance is burned in O 2, the
temperature of the calorimeter increases by 1.62
K. What is the energy of reaction ( rU) in kJ/mol?
A. -0.118
B. -18.3
C. -1440
D. -3770
41

Answer
D. -3770 kJ/mol
qr = -Ccal Tcal = -(13.0 kJ/K)(1.62 K) = -21.06
kJ
It took 1.151 g to generate that much heat, so
qr,m = - 18.30 kJ/g
where the subscript m represents per unit

mass

The molar mass is 205.9 g/mol, so


rU = (-18.30 kJ/g)(205.9 g/mol)

= -3770 kJ/mol
42

Enthalpy
Our second energy state function

43

Enthalpy
Symbol: H
Change in enthalpy, H
Change in enthalpy on reaction, rH
Relationship to U
H = U + PV

Relationship to q
U = qv (heat for constant volume process)
H = qP (heat for constant pressure process)
Since chemical reactions are often performed at

constant pressure, H tends to be used more than U


44

Enthalpy and heat


Starting with the definition,
H = U + PV
If a change happens at constant pressure
H = U + PV
For a constant-pressure process occurring at
equilibrium with the surroundings,
U = qP + w = q PV
Substituting
H = q PV + PV = qP

45

Endothermic vs
Exothermic
Endothermic process:
H > 0
Heat is taken in from the surroundings
Exothermic process
H < 0
Heat is released to surroundings

46

Source of Confusion
Exothermic reactions release heat
Combustion is exothermic
Temp of combusting system rises as reaction
proceeds
If system releases heat, shouldnt temp
decrease?

47

Endothermic reaction
Ba(OH)2.8H2O(s) + 2 NH4SCN(s)
Ba(SCN)2(s) + 10 H2O(l)
+ 2 NH3(g)

48

Source of Confusion
Tables of H values for processes at 1 atm

and 298K

Initial state: reactants at 1 atm and 298K


Final state: products at 1 atm and 298K

For exothermic reaction, heat has to be

removed to get products down to 298K


For endothermic reaction, heat has to be
added to warm products up to 298K

49

Endothermic example
Ba(OH)2(s)

NH4SCN(s)
q

25C

<25C

25C

Surr = 25C

Surr = 25C

Surr = 25C

Initial state: reactants at 25C


Mix and reaction cools (allowing heat to enter)
Final state: products warm to 25C (endothermic,

H>0)

50

A-ha!

51

Another source of
confusion
The mol-1 in rH
e.g. 4 Fe(s) + 3 O2(g) 2 Fe2O3(s) rH = -1648.4 kJ/mol
per mole of what?

Per mole of reaction


When 4 moles of Fe(s) react with 3 moles of O2(g) to

produce 2 moles of Fe2O3(s), that is called 1 mole of


reaction

rH must be accompanied by a stoichiometric

reaction
Otherwise, the per mole does not make sense

Reaction + rH called thermochemical equation


52

Oingo boingo!

53

Constant Pressure
Calorimetry
Constant V calorimetry yielded rU
recall: rU = qv

Constant P calorimetry yields rH


recall: rH = qP

54

A crude calorimeter
Insulated
2 Styrofoam cups & cork cap
Loose cap
equilibrium with atmosphere
Thermometer & stirring rod
Measure temp changes for

aqueous reactions &


calculate heat
Assume Ccal = mH2OCs,H2O
55

Example
HCl(aq) + NaOH(aq) NaCl(aq) + H2O(l)
50.0 mL of 1.00 M HCl are added to

50.0 mL of 1.00 M NaOH in a


calorimeter
Temp increases from 21.0 to 27.5C.
What is rH in kJ/mol, assuming no
heat loss and that the specific heat
of the solution is the same as for
water?
Cs,H20 = 4.184 J g-1 K-1, H2O = 1.00 g/mL

56

Answer
The reaction takes place under constant P
Hrxn = -qH2O = -mH20Cs,H2OT
T = (27.5-21.0)C = 6.5C = 6.5 K
mH2O = H2OVH2O = (1.00 g/mL)(100 mL) = 100 g
Hrxn = -(100 g)(4.18 J/g/K)(6.5 K) = -2.7 kJ
Hrxn in molar units:
Moles HCl = (50.010-3 L)(1.00 mol/L) = 50.0103 mol
Hrxn = (-2.7 kJ)/(5010-3 mol) = -54 kJ/mol
57

Hesss Law

58

Hesss Law
If a reaction is carried out in a series of steps, rH is
the sum of all the rHs of the individual steps

Consequence of H being a state function


H does not depend on
Number of steps
Nature of the steps

Tabulated rH can be used to calculate the rH

of a reaction that does not appear in the table


59

Enthalpy arithmetic
If thermochemical equation multiplied by a

factor, the enthalpy must also be multiplied


O2(g) + 2 H2(g) 2 H2O(l)
rH = -572 kJ/mol
O2(g) + H2(g) H2O(l)
rH = -286 kJ/mol
If thermochemical equation is reversed,
enthalpy is multiplied by -1
H2O(l) O2(g) + H2(g)
rH = +286 kJ/mol
Recall concept of per mole of reaction
60

Example
What is the enthalpy of combustion of C 3H6 (g) if
C3H6(g) + H2(g) C3H8(g)

H = -124 kJ

C3H8(g) + 5O2(g) 3CO2(g) + 4H2O(l) H =


-2220 kJ
O2(g) + 2 H2(g) 2 H2O(l)
H = -572 kJ
Reaction: C3H6 (g) + 9/2 O2 (g) 3 CO2 (g) + 3
H2O (l)
61

Example
Rxn: C3H6 (g) + 9/2 O2 (g) 3 CO2 (g) + 3 H2O (l)
produces 1 fewer moles H2O than C3H8

One path can be imagined in 3 steps:


Starting with C3H6, hydrogenate to form C3H8
Burn the C3H8 with oxygen
Decompose one of the product H2O back to O2

& H2
62

Enthalpy Diagram
C3H6+H2 TotalReaction:
1
C
H
+H
+5O
3CO
+3H
O+
/2O2+H2
3
6
2
2
2
2
+5O2

Enthalpy

C3H8+5O2

NetReaction:
C3H6+9/2O23CO2+3H2O

3CO2+3H2O
+1/2O2+H2
3CO2+4H2O
63

Example
Formal steps in the reaction:
C3H6 (g) + H2 (g) C3H8 (g)
rH = -124 kJ
9
/
C3H8 (g) + 25O2 (g) 3 CO2 (g) 3+ 4 H2O (l) rH = -2220
kJ
H2O(l) 1/2 O2 (g) + H2(g)
rH = +286 kJ
C3H6 (g) + 9/2O2 (g) 3 CO2 (g) + 3 H2O (l) rH = -2058 kJ
Blue reaction reversed and divided by 2
rH for blue equn found by multiplying given rH by -1/2

64

LC: Hesss Law


The reaction of acetylene (C2H2) with H2(g) can produce
either ethylene (C2H4), rH = 175.7 kJ/mol, or ethane
(C2H6), rH = 312.0 kJ/mol. The rH for the reaction of
ethylene with hydrogen to form ethane is:
A.
B.
C.
D.

+ 487.7 kJ/mol of C2H4


+ 136.3 kJ/mol of C2H4
136.3 kJ/mol of C2H4
487.7 kJ/mol of C2H4

Hint: start by writing out the full thermochemical equations (all three)
65

Hesss Law example


The hydrogenation reactions are:
C2H2 (g) + H2 (g) C2H4 (g)
rH = -175.7
kJ/mol
C2H2 (g) + 2H2 (g) C2H6 (g)
rH = -312.0
kJ/mol
We want C2H4 as the reactant, so reverse first
rxn
C2H4 (g) C2H2 (g) + H2 (g) rH = +175.7 kJ/mol
66

Hesss Law example


Add the reversed reaction to second:
C2H4 (g) C2H2 (g) + H2 (g)
kJ/mol
C2H2 (g) + 2H2 (g) C2H6 (g)
kJ/mol
C2H4 (g) + H2 (g) C2H6 (g)
kJ/mol

rH = +175.7
rH = -312.0
rH = -136.3

rH = rHethane - rHethylene
= -312.0 kJ/mol - (-175.3 kJ/mol)
= -136.3 kJ/mol (answer C)

67

Hesss Law and H of


formation
Standard enthalpy of formation, fH, is

the rH that produces 1 mol of a product and


only that product from its elements with all
participants in their standard states
The standard state is the most stable form at

1 bar pressure and temperature of interest


(usually 298 K)
fH of any element in its standard state is zero
Once the fH values of a large number of

compounds are known and tabulated, rH for


other reactions can be calculated

68

Using fH to Calculate
rH

69

70

71

LC: rH
What is the standard enthalpy of reaction for
the photosynthesis of glucose:
6 CO2 (g) + 6 H2O (l) C6H12O6 (s) + 6 O2 (g)
fH
fH
fH
fH

(glucose) = -1273 kJ/mol


(CO2) = -393.5 kJ/mol
(H2O) = -285.8 kJ/mol
(O2) = 0

72

Answer
rH = fH (glucose) + 6fH (O2)
- 6fH (CO2) 6fH (H2O)
= -1273 + 6(0) - 6(-393.5) - 6(-285.8)
= 2803 kJ/mol

73

Why does it work?


Special case of Hesss Law:
6 C(gr) + 3 O2(g) + 6 H2(g) C6H12O6(s)
fH=-1273 kJ
6 H2O (l) 6 H2 (g) + 3 O2 (g)
-6fH =
+1714.8 kJ
6 CO2 (g) 6 C (gr) + 6 O2
-6fH =
+2361.0 kJ
6 CO2 (g) + 6 H2O (l) C6H12O6 (s) + 6 O2 (g)
rH = +2803 kJ

74

Enthalpy Diagram

6H2O
6CO2

H=+23
61.

0kJ

Enthalpy

H=+
1714
.8kJ

6H2O+
6C+6O2

kJ
73
12
=
H

6H2+3O2+
6C+6O2

2
+

=
H

C6H12O6
+6O2

J
k

3
80

75

Summary
Energy
Internal energy, heat, and work
Heat capacity & heat transfer
P-V work
State functions vs path functions
Constant volume heat and energy changes

Enthalpy
Constant pressure calorimetry
Hesss Law
Enthalpy diagrams
Enthalpy of reaction & formation
76

Suggested Exercises
Review questions 1-29
Problems by topic 37, 39, 43, 45, 49, 53, 55,

57, 59, 63, 67, 71, 73, 75, 77, 79, 81, 83, 89,
117, 123, 133, 137, 139, 141

77

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