5

Energy & Chemistry

Potential Energy
8

2 H2(g) + O2(g) -->

--> on the Atomic Scale
2 H2O(g) + heat and light
• Positive and
This can be set up to negative particles
(ions) attract one
provide ELECTRIC another.
ENERGY in a fuel cell.
cell. • Two atoms can
bond
Oxidation:
• As the particles
---> 4 H+ + 4 e-
2 H2 ---> attract they have a
lower potential
Reduction: energy
4 e- + O2 + 2 H2O --->
---> 4 OH- CCR, page 845

11

Internal
Internal Energy
Energy (E)
(E)
17

Energy
Energy &
& Chemistry
Chemistry
All of thermodynamics depends
• PE + KE = Internal energy (E or U) on the law of
• Int. E of a chemical system
CONSERVATION OF ENERGY.
ENERGY.
12

Internal
Internal Energy
Energy (E)
(E)

depends on • PE
PE + KE =
= Internal energy (E or U)

• The total energy is unchanged

Q uickTime™ and a

• number of particles
Graphics decomp ressor
are need ed to s ee th is p ict ure.

• type of particles in a chemical reaction.

• temperature • If PE of products is less than
reactants, the difference must
be released as KE.

Specific
Specific Heat
Heat Capacity
21

UNITS
UNITS OF
OF ENERGY
ENERGY
19
Capacity
1 calorie = heat required to
raise temp. of 1.00 g of How much energy is transferred
H2O by 1.0 oC. due to T difference?
1000 cal = 1 kilocalorie = 1 The heat (q) “lost”
lost” or “gained”
gained” is
kcal related to
1 kcal = 1 Calorie (a food a) sample mass
“calorie”
calorie”) b) change in T and
But we use the unit called c) specific heat capacity
the JOULE James Joule
1 cal = 4.184 joules 1818-
1818-1889 Specific heat capacity =
heat lost or gained by substance (J)
(mass, g)(T change, K)

Heat
Heat &
& Changes
Changes of
of State
30
State Chemical Reactivity
31

How much heat is required to melt 500. g of ice What drives chemical reactions? How do they
and heat the water to steam at 100 oC? occur?
1. To melt ice The first is answered by THERMODYNAMICS and
q = (500. g)(333 J/g) = 1.67 x 105 J the second by KINETICS.
KINETICS.
Have already seen a number of “driving forces”
forces”
2. To raise water from 0 oC to 100 oC for reactions that are PRODUCT-
PRODUCT-FAVORED.
FAVORED.
q = (500. g)(4.2 J/g•
J/g•K)(100 - 0)K = 2.1 x 105 J • formation of a precipitate
3. To evaporate water at 100 oC • gas formation
• H2O formation (acid-
(acid-base reaction)
q = (500. g)(2260 J/g) = 1.13 x 106 J
• electron transfer in a battery
4. Total heat energy = 1.51 x 106 J = 1510 kJ
 39 40

ENTHALPY ENTHALPY
Most chemical reactions occur at constant P, so ∆H = Hfinal - Hinitial

IfIfH
Hfinal > H initial then
then ∆∆H
H is
is positive
Heat transferred at constant P = qpp final > Hinitial positive
Process is ENDOTHERMIC
Process is ENDOTHERMIC
qpp = ∆H
∆H where H = enthalpy
IfIfH
Hfinal < H initial then
then ∆∆H
H is
is negative
and so ∆E=∆
∆E H + w (and w is usually small)
∆H final < Hinitial negative
∆H = heat transferred at constant P ≈ ∆
∆H E
∆E
Process is EXOTHERMIC
Process is EXOTHERMIC
∆H = change in heat content of the system
∆H
∆
∆HH = Hfinal - Hinitial

46

USING ENTHALPY 
∆∆H
43
H along
along one
one path
path ==

∆∆H
H along
along another
another path
path
Making H2O from H2 involves two steps.
H2(g) + 1/2 O2(g) --->
---> H2O(g) + 242 kJ • This equation is valid because
H2O(g) --->
---> H2O(liq) + 44 kJ ∆H is a STATE FUNCTION
----------------------------------------------------------------------- • These depend only on the state
of the system and not on how
H2(g) + 1/2 O2(g) -->
--> H2O(liq) + 286 kJ the system got there.
Example of HESS’
HESS’S LAW—
LAW— • V, T, P, energy — and your bank
account!
If a rxn.
rxn. is the sum of 2 or more others, • Unlike V, T, and P, one cannot
the net ∆H is the sum of the ∆H’s of measure absolute H. Can only
the other rxns.
rxns. measure ∆H.

47
Enthalpy Values 48

Standard Enthalpy Values Depend

Depend onon how
how the
the reaction
reaction is
is written
written and
and on
on phases
phases
Most ∆H values are labeled ∆Ho of
of reactants
reactants and
and products
products
Measured under standard conditions H2(g) + 1/2 O2(g) -->
--> H2O(g)
P = 1 bar = 105 Pa = 1 atm /1.01325 ∆H˚ = -242 kJ
Concentration = 1 mol/L 2 H2(g) + O2(g) -->
--> 2 H2O(g)
T = usually 25 oC ∆H˚ = -484 kJ
with all species in standard states H2O(g) --->
---> H2(g) + 1/2 O2(g)
e.g., C = graphite and O2 = gas
∆H˚ = +242 kJ
H2(g) + 1/2 O2(g) -->
--> H2O(liquid)
∆H˚ = -286 kJ

49
∆Hfo, standard molar 50

Standard Enthalpy Values enthalpy of formation

NIST (Nat’
(Nat’l Institute for Standards and Enthalpy change when 1 mol of
Technology) gives values of compound is formed from the
∆Hfo = standard molar enthalpy of corresponding elements under
formation standard conditions
— the enthalpy change when 1 mol of H2(g) + 1/2 O2(g) -->
--> H2O(g)
compound is formed from elements under ∆Hfo (H2O, g)= -241.8 kJ/mol
standard conditions.
By definition,
∆Hfo = 0 for elements in their
standard states.
 Using Standard Enthalpy Values 51
Using Standard Enthalpy Values 52

Use ∆H˚’s to calculate enthalpy change for

H2O(g) + C(graphite) -->
--> H2(g) + CO(g)

H2O(g) + C(graphite) -->

--> H2(g) + CO(g) From reference books we find
• H2(g) + 1/2 O2(g) -->
--> H2O(g) ∆Hf˚ = - 242 kJ/mol
• C(s) + 1/2 O2(g) -->
--> CO(g) ∆Hf˚ = - 111 kJ/mol

(product is called “water gas”

gas”)

Using Standard Enthalpy Values 53 54

Using Standard Enthalpy Values

H2O(g) -->
--> H2(g) + 1/2 O2(g) ∆Ho = +242 kJ
--> CO(g) ∆Ho = -111 kJ
C(s) + 1/2 O2(g) --> Calculate ∆H of
reaction?
--------------------------------------------------------------------------------
In general, when ALL
H
H22O(g)
O(g) +
+ C(graphite)
C(graphite) -->
-->H
--> H22(g)
(g) +
+ CO(g)
CO(g) enthalpies of formation are
∆Hoo
∆H net = +131 kJ
net = +131 kJ known:
To convert 1 mol of water to 1 mol each of H2
and CO requires 131 kJ of energy. ∆
∆H =  ∆H oo (products) -  ∆H oo (reactants)
rxn =  ∆Hff (products) -  ∆Hff (reactants)
Hoorxn
The “water gas”
gas” reaction is ENDOthermic.
ENDOthermic. Remember that ∆ always = final – initial

59
Measuring
Measuring Heats
Heats of
of Reaction
Reaction 60

Measuring
Measuring Heats
Heats of
of Reaction
Reaction CALORIMETRY
CALORIMETRY
CALORIMETRY
CALORIMETRY
Step 1 Calc. heat transferred from reaction to water.
q = (4.184 J/g•
J/g•K)(1200 g)(8.20 K) = 41,170 J
Calculate heat of combustion of octane.
C8H18 + 25/2 O2 -->
--> 8 CO2 + 9 H2O Step 2 Calc. heat transferred from reaction to bomb.
• Burn 1.00 g of octane q = (bomb heat capacity)(∆
capacity)(∆T)
• Temp rises from 25.00 to 33.20 oC = (837 J/K)(8.20 K) = 6860 J

• Calorimeter contains 1200 g water Step 3 Total heat evolved

• Heat capacity of bomb = 837 J/K 41,170 J + 6860 J = 48,030 J
Heat of combustion of 1.00 g of octane = - 48.0 kJ

Thermochemical Equations
Thermochemical Equations
• The stoichiometric coefficients always refer to the number
of moles of a substance • The physical states of all reactants and products must be
specified in thermochemical equations.
H2O (s) H2O (l) H = 6.01 kJ
H2O (s) H2O (l) H = 6.01 kJ
• If you reverse a reaction, the sign of H changes H2O (l) H2O (g) H = 44.0 kJ
H2O (l) H2O (s) H = -6.01 kJ
How much heat is evolved when 266 g of white
• If you multiply both sides of the equation by a factor n, phosphorus (P4) burn in air?
then H must change by the same factor n. P4 (s) + 5O2 (g) P4O10 (s) H = -3013 kJ

2H2O (s) 2H2O (l) H = 2 x 6.01 = 12.0 kJ 1 mol P4 3013 kJ

266 g P4 x x = 6470 kJ
123.9 g P4 1 mol P4

6.3 6.3
The specific heat (s) of a substance is the amount of heat (q)
required to raise the temperature of one gram of the
How much heat is given off when an 869 g iron bar cools
substance by one degree Celsius. from 940C to 50C?
The heat capacity (C) of a substance is the amount of heat
(q) required to raise the temperature of a given quantity (m) s of Fe = 0.444 J/g • 0C

of the substance by one degree Celsius. t = tfinal – tinitial = 50C – 940C = -890C
C = ms q = mst = 869 g x 0.444 J/g • 0C x –890C = -34,000 J

Heat (q) absorbed or released:

q = mst
q = Ct
t = tfinal - tinitial

6.4 6.4

Constant-Volume Calorimetry
Constant-Pressure Calorimetry

qsys = qwater + qbomb + qrxn

qsys = 0 qsys = qwater + qcal + qrxn
qrxn = - (qwater + qbomb) qsys = 0
qrxn = - (qwater + qcal)
qwater = mst
qwater = mst
qbomb = Cbombt
qcal = Ccalt
Reaction at Constant V
Reaction at Constant P
H = qrxn H = qrxn
H ~ qrxn
No heat enters or leaves! No heat enters or leaves!
6.4 6.4

Because there is no way to measure the absolute value of

the enthalpy of a substance, must I measure the enthalpy
change for every reaction of interest?

Establish an arbitrary scale with the standard enthalpy of

formation (H0f ) as a reference point for all enthalpy
expressions.

Standard enthalpy of formation (H0f) is the heat change

that results when one mole of a compound is formed from
its elements at a pressure of 1 atm.

The standard enthalpy of formation of any element in its

most stable form is zero.
H0f (O2) = 0 H0f (C, graphite) = 0
H0 f (O3) = 142 kJ/mol H0f (C, diamond) = 1.90 kJ/mol
6.4 6.5

0
The standard enthalpy of reaction (Hrxn ) is the enthalpy of
a reaction carried out at 1 atm.

aA + bB cC + dD

H0
rxn = [ cH0f (C) + dH0f (D) ] - [ aH0
f (A) + bH0
f (B) ]

rxn =  nH f (products) -  mHf (reactants)

H0 0 0

Hess’s Law: When reactants are converted to products,

the change in enthalpy is the same whether the reaction
takes place in one step or in a series of steps.

(Enthalpy is a state function. It doesn’t matter how you get

there, only where you start and end.)
6.5
 6.5

Benzene (C6H6) burns in air to produce carbon dioxide and

liquid water. How much heat is released per mole of
Calculate the standard enthalpy of formation of CS 2 (l)
benzene combusted? The standard enthalpy of formation
given that:
of benzene is 49.04 kJ/mol.
C(graphite) + O2 (g) CO2 (g) H0rxn = -393.5 kJ
S(rhombic) + O2 (g) SO2 (g) H0rxn = -296.1 kJ 2C6H6 (l) + 15O2 (g) 12CO2 (g) + 6H2O (l)
CS2(l) + 3O2 (g) CO2 (g) + 2SO2 (g) Hrxn
0 = -1072 kJ
H0rxn =  nH0f (products) -  mHf0 (reactants)
1. Write the enthalpy of formation reaction for CS 2

C(graphite) + 2S(rhombic) CS2 (l) H0rxn = [ 12H0f (CO2) + 6H0f (H2O)] - [ 2H0f (C6H6)]
2. Add the given rxns so that the result is the desired rxn.
H0rxn = [ 12x–393.5 + 6x–187.6 ] – [ 2x49.04 ] = -5946 kJ
C(graphite) + O2 (g) CO2 (g) H0rxn = -393.5 kJ
2S(rhombic) + 2O2 (g) 2SO2 (g) H0rxn = -296.1x2 kJ -5946 kJ
= - 2973 kJ/mol C6H6
+ CO2(g) + 2SO2 (g) 2 mol
CS2 (l) + 3O2 (g) Hrxn
0 = +1072 kJ

C(graphite) + 2S(rhombic) CS2 (l)

6.5 H 0 = -393.5 + (2x-296.1) + 1072 = 86.3 kJ
rxn 6.5

Enthalpy and the First Law of Thermodynamics

Thermodynamics
E = q + w
E = q + w
At constant pressure, q = H and w = -PV
E is the change in internal energy of a system
q is the heat exchange between the system and the surroundings E = H - PV
w is the work done on (or by) the system H = E + PV
w = -PV when a gas expands against a constant external pressure

6.7 6.7