John W.

Moore
Conrad L. Stanitski

http://academic.cengage.com/chemistry/moore

Chapter 4
Energy and Chemical Reactions

Stephen C. Foster • Mississippi State University

The Nature of Energy
Energy (E) = the capacity to do work.

Work (w) occurs when an object moves against a

resisting force:

w = −(resisting force) x (distance traveled)

w = −F d

All energy is either Kinetic or Potential energy.

The Nature of Energy
Kinetic energy (Ek) - Energy of motion
 macroscale = mechanical energy
 random nanoscale = thermal energy
 periodic nanoscale = acoustic energy

Ek = ½mv2 (m = mass, v = velocity of object)

Potential energy (Ep) – Energy of position. Stored E.

It may arise from:
• gravity: Ep = m g h (mass x gravity x height).
• charges held apart.
• bond energy.
Energy Units
joule (J) - SI unit (1 J = 1 kg m2s-2)

2.0 kg mass moving at 1.0 m/s (~2 mph):

Ek = ½ mv2 = ½ (2.0 kg)(1.0 m/s)2

= 1.0 kg m2 s-2
= 1.0 J

1 J is a relatively small amount of energy.

1 kJ (1000 J) is more common in chemical problems.
Energy Units
calorie (cal)
Originally: “Energy needed to heat of 1g of water
from 14.5 to 15.5 °C.”

Now: 1 cal = 4.184 J (exactly)

Dietary Calorie (Cal)

“big C” calorie
Used on food products.
1 Cal = 1000 cal = 1 kcal = 4.184 1 sachet (16 kJ) is…
kJ …2 tsps of sugar (140 kJ)
Energy Units
energy
Power = time

SI unit: 1 watt (W) = 1 J s-1

A 60-W incandescent bulb is used for 6.0 hours. How

much energy does it consume?
60 m 60 s
E = power x time = 60 J s (6.0 h)
-1
1h 1m

E = 1.3 x 106 J = 1.3 MJ

Conservation of Energy
“Energy can neither be created nor destroyed”.

It can only change form.

Total E of the universe is constant.

Also called the 1st Law of Thermodynamics.

Conservation of Energy

A diver:
a) Has Ep due to macroscale position.
b) Converts Ep to macroscale Ek.
c) Converts Ek,macro to Ek,nano (motion of water, heat)
Energy & Working
If an object moves against a force, work is done.
• Lift a book
 you do work against gravity. The book’s Ep increases.

• Drop the book:

 Ep converts into Ek
 The book does work pushing the air aside.

• The book hits the floor

 no work is done on the floor (it does not move).
 Ek converts to a sound wave and T of the book and floor
increase (Ek converts to heat).
Energy, Temperature & Heating
Temperature is a measure of the
thermal energy of a sample.

Thermal energy
• E of motion of atoms, molecules, and
ions.
• Atoms of all materials are always in
motion.
• Higher T = faster motion.
Energy, Temperature & Heating
Heat
• Thermal E transfer caused by a T difference.
• Heat flows from hotter to cooler objects until
they reach thermal equilibrium (have equal T ).
Keeping Track of Energy Transfers
System = the part of the universe under study
 chemicals in a flask.
 my textbook.

Surroundings = rest of the universe (or as much as

needed…)
 the flask.
 perhaps the flask and this classroom.
 perhaps the flask and all of the building, etc.

Universe = System + Surroundings

Keeping Track of Energy Transfers
Internal energy = sum of the individual energies of all
nanoscale particles in the system.

Einternal includes all nanoscale Ek and Ep. A larger

sample (larger system) will have larger Einternal

Nanoscale Ek = thermal energy

Nanoscale Ep:
 ion/ion attraction or repulsion
 nucleus/electron attraction
 proton/proton repulsion …..
Keeping Track of Energy Transfers
Internal energy depends on
• Temperature
 higher T = larger Ek for the nanoscale particles.

• Type of material
 nanoscale Ek depends upon the particle mass.
 nanoscale Ep depends upon the particle type(s).

• Amount of material
 number of particles.
 double sample size, double Einternal, etc.
 Calculating Thermodynamic Changes
Energy change = final E – initial E
ΔE = Efinal – Einitial
“Change in”

Systems can gain or lose E:

SURROUNDINGS SURROUNDINGS

SYSTEM SYSTEM
Efinal Einitial

ΔE > 0 E in ΔE < 0 E out

Einitial Efinal

ΔE positive: internal energy ΔE negative: internal energy

increases decreases
Conservation of Energy & Reactions
No subscript? Refers to the system: E = Esystem
E is transferred by heat or by work.
Conservation of energy becomes: ΔE = q + w
heat work
SURROUNDINGS

SYSTEM

Heat transfer in Heat transfer out

q>0 q<0
ΔE = q + w
Work transfer in Work transfer out
w>0 w<0

A positive q or w increases E
• Negative values decrease E
Energy Changes
A motor does 50.2 J of work on its surroundings while
transferring 90.1 J of heat transfer to its surroundings.
Calculate the change in the energy during this process.
Assume the motor is the system

Work done on surroundings (by the system) w = -50.2 J

Heat from system to surroundings q = +90.1 J

ΔE = q + w
ΔE = -50.2 J -90.1 J = J
Heat Capacity
Heat capacity = E required to raise the T of an object
by 1°C. Varies from material to material.

Specific heat capacity (c)

• E needed to heat 1 g of substance by 1°C.

Molar heat capacity (cm)

• E needed to heat 1 mole of substance by 1°C.
Heat Capacity
For other amounts or for other T changes:

Heat required = mass x specific heat x ΔT

q = m c ΔT
or…

Heat required = moles x molar heat capacity x ΔT

q = n cm ΔT
Heat Capacity
Substance c (J g-1 °C-1) cm (J mol-1 °C-1)
Elements
C (graphite) 0.720 8.65
Al(s) 0.902 24.3
Fe(s) 0.451 25.1
Cu(s) 0.385 24.4
Au(s) 0.129 25.4
Compounds
NH3(ℓ) 4.70 80.1
H2O(ℓ) 4.184 75.3
H2O(s) 2.06 37.1
CCl4(ℓ) 0.861 132.
CCl2F2(ℓ) 0.598 72.3
Common solids
wood 1.76
concrete 0.88
glass 0.84
granite 0.79
Heat Capacity
How much energy will be used to heat 500.0 g of iron
from 22°C to 55°C? cFe = 0.451 J g-1 °C-1.

Heat required = q = m c ΔT
q = 500.0 g (0.451 J g-1 °C-1)(55 − 22)°C
q = 7442 J = +7.4 kJ

+ sign, E added to the system (the iron)

Heat Capacity
24.1 kJ of energy is lost by a 251 g aluminum block. If
the block is initially at 125.0°C what will be its final
temperature? (cAl = 0.902 J g-1 °C-1)
q = m c ΔT
ΔT = q / (m c)
Cooling, q is negative:
ΔT = −24.1 x 103 J
251 g(0.902 J g-1 °C-1)
ΔT = Tfinal – Tinital = −106.4 °C

Thus Tfinal = ΔT + Tinital = −106.4 + 125.0°C = 19°C

Heat Capacity
A 215 g block of Cu at 505.0°C is plunged into 1.000 kg
of water (T = 23.4 °C) in an insulated container. What
will be the final equilibrium T of the water and the Cu?
(cCu = 0.385 J g-1 °C-1, cH2O = 4.184 J g-1 °C-1)

q = m c ΔT

qCu = (215. g)(0.385 J g-1 °C-1)(Tfinal− 505.0)

qH2O = (1000. g)(4.184 J g-1 °C-1)(Tfinal− 23.4)

qCu + qH2O = 0 (conservation of E)
qH2O = -qCu
Heat Capacity
215 g Cu (505.0°C) + 1000. g H2O (23.4 °C). Final T ?

qH2O = -qCu

4184(Tfinal – 23.4) = -82.78(Tfinal – 505.0)

(4184 + 82.78)Tfinal = 41804 + 97906

Tfinal = 32.7°C

(Note: Tfinal must be between Thot and Tcold)

Conservation of Energy & Changes of State
During freezing (or melting)
• Substance loses (or gains) E, but…
• T remains constant.

50
Example:
Temperature (°C)
25

Convert 1 g of ice Ice is melting. T

remains at 0°C
at -50°C to water at Water warms
from 0 to 50°C
+50°C
-25 0

Ice warms from -50

to 0°C
-50

0 100 200 300 400 500 600

Quantity of energy transferred (J)
Conservation of Energy & Changes of State
As a liquid boils its T remains constant
• When P = 1 atm, water boils at 100 °C
• the steam produced will inflate a balloon
 Conservation of Energy & Changes of State
When heat is: Added to a system
 q is positive
 the change is endothermic

Removed from a system

 q is negative
 the change is exothermic.

Water Boils: H2O(ℓ)  H2O(g) endothermic

Steam Condenses: H2O(g)  H2O(ℓ) exothermic

Work occurs as the sample expands or contracts.

Overall: ΔE = q + w
Energy & Working
The amount of work is proportional to the volume
change:
w = -PΔV (for a reaction at constant P)
In chemical processes, work occurs whenever
expansion occurs.

The amount of work is larger if one or more gases

are produced or react away.
• ΔV is relatively small whenever solids and liquids
are produced or removed.
• ΔV is relatively large if gases are involved.
Melting (Fusion) & Freezing
ΔfusionH (or ΔfusH) is the heat required (at constant P)
to melt a solid.

Change Name value for H2O (J/g)

solid → liq enthalpy of fusion 333
liq → solid enthalpy of freezing −333

Note: ΔfusH = − ΔfreezingH

qfusion = −qfreezing
Vaporization & Condensation
ΔvapH = qP = heat to vaporize a liquid (at constant P)

Change Name value for H2O (J/g)

liq → gas enthalpy of vaporization 2260
gas → liq enthalpy of condensation −2260

Note: ΔvapH = − ΔcondensationH

qvap = −qcondensation
State Functions & Path Independence
State functions
Always have the same value whenever the system is in
the same state.

Two equal mass samples of water produced by:

1. Heating one from 20°C to 50°C. State
2. Cooling the other from 100°C to 50°C. functions
HE
have identical final H (and V, P, E…). PV
T etc.
State function changes are path independent.
ΔH = Hfinal – Hinitial is constant.
Reaction Enthalpies for Chemical Reactions
ΔH = qP can be added to a balanced equation.
CH4(g) + 2 O2(g) → CO2(g) + 2 H2O(g) ΔrH° = -803.05 kJ/mol
CH4(g) + 2 O2(g) → CO2(g) + 2 H2O(ℓ) ΔrH° = -890.36 kJ/mol

ΔrH° is the standard reaction enthalpy change

 P = 1 bar.
 T must be stated (if it isn’t, assume 25°C).
 ΔrH° is for the reaction as written.
 Burn 1 mol of CH4 with 2 mol O2 to form 2 mol of liquid
water and release 890 kJ of heat
 ΔrH° depends upon physical states: H2O(ℓ) vs. H2O(g)
Reaction Enthalpies for Chemical Reactions
The thermite reaction produces tremendous heat:
2 Al + Fe2O3 → Al2O3 + 2 Fe ΔrH° = – 851.5 kJ/mol
How much heat is released when 10.0 g of Al reacts
with excess Fe2O3 at constant P ?

nAl = 10.0 g / 26.982 g mol-1

= 0.3706 mol Al
2 mol Al ≡ 1 mol reaction
1 mol reaction ≡ -851.5 kJ
-851.5 kJ
qp = 0.3706 mol Al = -158 kJ
2 mol Al
Where Does the Energy Come From?
Bond Enthalpy (bond energy)
Equals the strength of 1 mole of bonds
• Always positive
 It takes E to break a bond
 Separated parts are less stable than the molecule.
 Less stable = higher E

• E is always released when a bond forms

 Product is more stable than the separated parts.
 More stable = lower E
Bond Enthalpies
During a chemical reaction:
Old bonds break: requires E (endothermic)
New bonds form: releases E (exothermic)

Both typically occur:

H2(g) + Cl2(g) → 2 H(g) + 2 Cl(g) → 2 HCl(g)

endothermic exothermic
ΔH= +678 kJ/mol ΔH= -862 kJ/mol
Bond Enthalpies
Overall, heat may be absorbed or released:
Exothermic reactions (ΔH < 0)

increasing enthalpy
• E is released.
• New bonds are more stable than the old, or
reactants
• More bonds are formed than broken. products

Endothermic reactions (ΔH > 0)

increasing enthalpy
• E is absorbed.
• New bonds are less stable than the old, or
products
• Fewer bonds are formed than broken reactants
Measuring Reaction Enthalpies
Heat transfers are measured with a calorimeter.
Common types:
• Bomb calorimeter.
• rigid steel container.
• filled with O2(g) and a small sample to be burnt.
• constant V, so qV = ΔrE

• Flame calorimeter.
• samples burnt in an open flame.
• constant P, so qp = ΔrH

• Coffee-cup calorimeter in lab (constant P).

Constant Volume Calorimetry
Bomb Calorimeter
Measure ΔT of the water. Constant V: q V = Δr E

Conservation of E:
qreaction + qbomb + qwater = 0

or
−qreaction = qbomb + qwater
with
qbomb = mcalccalΔT = CcalΔT
A constant for a calorimeter
Constant Volume Calorimetry
Octane (0.600 g) was burned in a bomb calorimeter containing
751 g of water. T increased from 22.15 °C to 29.12 °C. Calculate
the heat evolved per mole of octane burned. Ccal = 895 J°C-1.
2 C8H18(ℓ) + 25 O2(g) → 16 CO2(g) + 18 H2O(ℓ)

qreaction + qbomb + qwater = 0

qbomb = CcalΔT = 895 J°C-1 (29.12 – 22.15)°C

= +6238 J

qwater = m c ΔT
= 751 g (4.184 J g-1 °C-1)(29.12 – 22.15)°C
= +2.190 x 104 J
Constant Volume Calorimetry
T = 22.15 → 29.12°C. Heat per mol octane (0.600 g) burned.
2 C8H18(ℓ) + 25 O2(g) →16 CO2(g) + 18 H2O(ℓ)

−qreaction = qbomb + qwater

−qreaction = +6238 J + 2.190 x 104 J

= 2.81 x 104 J
= 28.1 kJ

qreaction = −28.1 kJ
Constant Volume Calorimetry
Octane (0.600 g)… Calculate the heat evolved per mole of octane burned

Molar mass of C8H18 = 114.23 g/mol.

nC8H18 = (0.600 g) / (114.23 g/mol)
= 0.00525 mol C8H18

Heat evolved /mol octane = -28.1 kJ

0.00525 mol

= -5.35 x 103 kJ/mol

= -5.35 MJ/mol
Constant Volume Calorimetry
Coffee-cup calorimeter
Nested styrofoam cups prevent heat exchange
with the surroundings.

Constant P. ΔT measured.
q = qp = ΔH

Assume the cups do not absorb heat.

(Ccal = 0 and qcal = 0)
Constant Volume Calorimetry
1.02 g of Mg was reacted with excess 1 M HCl(aq)
(255.0 g) in a coffee-cup calorimeter. Tsoln rose from
22.0 to 41.6 °C. cHCl = 3.90 J g-1°C-1 . Complete:
Mg(s) + 2 HCl(aq)  H2(g) + MgCl2(aq) ΔrH° = ?

qsoln = msolnc ΔT (msoln = macid + mMg )

= 256.0 g (3.90 J g-1 °C-1)(41.6 − 22.0)°C
= 1.957 x 104 J

Conservation of E: qsoln + qrxn = 0

qrxn = -qsoln qrxn = -19.57 kJ = ΔrH°

Constant Volume Calorimetry
1.02 g Mg + 255.0 g of acid. T: 22.0 → 42.5 °C. Molar ΔrH° = ?

qrxn = -19.57 kJ = ΔrH° for 1.02 g

MMg = 24.31 g mol-1

For 1 mol
-19.57 kJ 24.31 g
ΔrH° = = -476 kJ exothermic
1.02 g 1 mol
Hess’s Law
“If the equation for a reaction is the sum of the
equations for two or more other reactions, then Δ rH°
for the 1st reaction must be the sum of the ΔrH° values
of the other reactions.”

Another version:
“ΔrH° for a reaction is the same whether it takes place
in a single step or several steps.”

H is a state function
Hess’s Law
Multiply a reaction, multiply ΔrH°.
Reverse a reaction, change the sign of ΔrH°
2 CO(g) + O2(g) → 2 CO2 (g) ΔrH° = −566.0 kJ/mol

Then
2 CO2(g) → 2 CO(g) + O2(g) ΔrH° = -1(-566.0 kJ/mol)
= +566.0 kJ/mol

4 CO2(g) → 4 CO(g) + 2 O2(g) ΔrH° = -2(-566.0 kJ/mol)

= +1132.0 kJ/mol
Hess’s Law
Use Hess’s Law to find kJ/mol for unknown reactions.

Example
It is difficult to measure ΔrH° for:
2 C(graphite) + O2(g)  2 CO(g)
Some CO2 always forms. Calculate ΔrH° given:

C(graphite) + O2(g)  CO2(g) ΔrH° = -393.5 kJ/mol

2 CO(g) + O2(g)  2 CO2(g) ΔrH° = -566.0 kJ/mol

No phase confusion… drop phases

Hess’s Law
Want: 2C + O2 → 2 CO ???
Have: A C + O2 → CO2 -393.5 kJ/mol
B 2CO + O2 → 2 CO2 -566.0 kJ/mol

+2 x A 2C + 2O2 → 2CO2 2(-393.5) = -787.0

−1 x B 2CO2 → 2CO + O2 -1(-566.0) = +566.0

2C + 2O2 + 2CO2 → 2CO2 + 2CO + O2 -221.0

2 C + O2 → 2 CO ΔrH° = -221.0 kJ/mol

Hess’s Law
Determine ΔH° for the production of coal gas:

2 C(s) + 2 H2O(g)  CH4(g) + CO2(g)

Using:
C(s) + H2O(g)  CO(g) + H2(g) ΔH° = 131.3 kJ/mol A
CO(g) + H2O(g)  CO2(g) + H2(g) ΔH° = -41.2 kJ/mol B
CH4(g) + H2O(g)  CO(g) + 3 H2(g) ΔH° = 206.1 kJ/mol C

No phase confusion… drop phases

Hess’s Law
Want: 2 C + 2 H2O → CH4 + CO2 ???
Have: A C + H2O → CO + H2 131.3 kJ/mol
B CO + H2O → CO2 + H2 -41.2 kJ/mol
C CH4 + H2O → CO + 3 H2 206.1 kJ/mol

+2 x A 2 C + 2 H2O → 2 CO + 2 H2 +262.6

-1 x C CO + 3 H2 → CH4 + H2O -206.1

+1 x B CO + H2O → CO2 + H2 -41.2
2C + 2H2O → CH4 + CO2 15.3 kJ/mol

(After cancelling and adding)

Standard Formation Enthalpies
Hess’s law problems often use a combustion or …

Formation reaction
Make 1 mol of compound from its elements in their
standard states.

H2 combustion:
2 H2(g) + O2(g) → 2 H2O(ℓ) ΔrH° = −571.66 kJ/mol
but the formation reaction is:
H2(g) + ½ O2(g) → 1 H2O(ℓ) ΔfH° = −285.83 kJ/mol
f = formation
Standard Formation Enthalpies
The standard state of an element is its most stable
form when P = 1 bar.

Some standard states (at 25 °C):

• Carbon = graphite (not diamond).
• Nitrogen = N2(g)

ΔfH° for any element in its standard state is zero.

(take 1 mol of the element and make… 1 mol of element)

ΔHf° (Br2(ℓ) ) = 0 at 25 °C
ΔHf° (Br2(g) ) ≠ 0 at 25 °C
Standard Formation Enthalpies
Appendix J (25°C) Compound ΔHf°, kJ/mol

Al2O3(s) aluminum oxide −1675.7

CaO(s) calcium oxide −635.09

Notes
• Most are negative CH4(g) methane −74.81
(formation releases E), C2H2(g) acetylene +226.73
but can be positive.
C2H4(g) ethylene +52.26
• If the physical state C2H6(g) ethane −84.68
changes, ΔfH° changes.
C2H5OH(l) ethanol −277.69

H2O(g) water vapor −241.818

H2O(l) liquid water −285.830

Standard Formation Enthalpies
ΔrH° ={(nproducts)(ΔfH°products)}
– {(nreactants)(ΔfH°reactants)}
Example
Calculate ΔrH° for:
CH4(g) + NH3(g)  HCN(g) + 3 H2(g)

ΔrH° = ΔfH°(HCN) + 3ΔfH°(H2) − ΔfH°(NH3) – ΔfH°(CH4)

= +134 + 3(0) – (-46.11) – (-74.85) = 255 kJ/mol

Fuels for Society & Our Bodies
Chemical Fuel – reacts exothermically with O2 in air.
A good fuel has weak bonds and/or forms strong product bonds.

Hydrazine
N2H4(g) + O2(g) → N2(g) + 2 H2O(g)
Ebond(kJ/mol) 160(NN), 391(NH) 498(OO) 946(NN) 467(OH)
1 NN 4 OH
4 NH 1 OO 1 NN (2 OH/molecule)

Emolecule 1724 498 946 1864

Ereagents 2222 2814

ΔE -592 kJ/mol
Fuels for Society & Our Bodies
Good fuels have large:
• Fuel value = (E released) / (mass of fuel in g)
• Energy density = (E released) / Vfuel

U.S. sources of E:
Mostly fossil fuels.
Fuels for Society & Our Bodies
Carbohydrates, Cx(H2O)y
Glucose (C6H12O6) fuels our bodies:
C6H12O6 + 6 O2 → 6 CO2 + 6 H2O ΔrH° = −2801.6 kJ/mol
(average carbohydrate =17 kJ/g or 4 Cal/g)

Excess glucose  fat. Fat is metabolized as needed:

2 C57H110O6 + 163 O2 → 114 CO2 + 110 H2O
ΔH° = −75,520 kJ/mol
tristearin
(42 kJ/g) (average fat = 38 kJ/g or 9 Cal/g)

Dietary protein yields 17 kJ/g or 4 Cal/g.

Fuels for Society & Our Bodies

Approximate Composition
Food per 100. g Caloric Value
Fat Carbohydrate Protein Cal/g kJ/g
Apple 0.5 13.0 0.4 0.59 2.47
Brownie with nuts 16.0 64.0 4.0 4.04 16.9
Cheese pizza 10.2 25.8 11.2 2.41 10.1
Green beans 0.0 7.0 1.9 0.38 1.60
Hamburger 30.0 0.0 22.0 3.60 15.06
Peanuts (unsalted) 50.0 21.4 28.6 5.71 23.91
Rice 1.0 77.6 8.2 3.47 14.52
Tomato sauce 0.0 4.8 1.6 0.24 1.01
Fuels for Society & Our Bodies
Basal metabolic rate (BMR) E to maintain a body at rest

• BMR depends on age, gender and body mass.

• 70-kg male averages 1750 Cal/day
• 70-kg female averages 1525 Cal/day
• ≈ 1 Cal kg-1 h-1.
• Active lifestyles require more energy
• Walking requires BMR x 2.5
• Playing basketball or soccer: BMR x 7