Ch.

6 - Thermochemistry
Ch.6.1: The Nature of Energy
Energy: An object’s capacity to perform work or produce heat
Work : force acting over a distance (W = F x d).
Heat : energy transferred between objects because of temperature difference.

Potential Energy: Energy due to position or composition (chemical bonds).

1
Kinetic Energy: Energy due to the motion of the object KE  mv 2
2
Law of Conservation of Energy: Energy can neither be created nor destroyed,
but can be converted between forms
The First Law of Thermodynamics: The total energy content of the universe is
constant
 E = q + W E = change in internal energy of a system

q = heat flowing into or out of the system

+q : energy is absorbed from the surroundings (endothermic)
-q : energy is released to the surroundings (exothermic)

W = work done by, or on, the system

+w : work is done on the system by the surroundings
-w : work is done by the system on the surroundings

Question 1: Determine the change in the internal energy for a system

undergoing an endothermic process in which 15.6 kJ of heat flows and where
1.4 kJ of work is done on the system.

E = (+15.6) + (+1.4) => E = + 17.0 kJ

 Work, Pressure,
and Volume
w   PV

Expansion Compression
+V (increase) -V (decrease)

-w results +w results

Esystem decreases Esystem increases

Work is done by the system Work is done on the system

on the surroundings by the surroundings

Q2: Calculate the work resulting from

w = - (15)(64 - 46) = - 270 atm-L
the expansion of a gas from 46 L to 64 L
at a constant external pressure of 15 atm. w = - 27351 J
1 L-atm = 101.3 J
Question 3: Which of the following performs more work? (1 L-atm = 101.3 J)
(a) A gas expanding against a pressure of 2.0 atm from 1.0 L to 4.0 L
(b) A gas expanding against a pressure of 3.0 atm from 1.0 L to 3.0 L

wa = - (2.0)(4.0 – 1.0) = - 6.0 atm-L = - 607.8 J

wb = - (3.0)(3.0 – 1.0) = - 6.0 atm-L = - 607.8 J

Question 4: Determine the sign of E for each of the following processes with
the listed conditions:
(a) An endothermic process that performs work on the surroundings.
a.1) work > heat  E : (+) or, (-)
E = +q + (-w)
a.2) work < heat  E : (+) or, (-)

(b) Work is done on a gas and the process is exothermic.

b.1) work > heat  E : (+) or, (-) E = - q + (+w)

b.2) work < heat  E : (+) or, (-)
 Energy Change in Chemical Processes
Chemical Reactions: Energy is absorbed to break chemical bonds & energy is
released when new bonds are formed.
Exothermic Reactions:
Reactions in which energy flows out of the system and to the surroundings
as the reaction proceeds.
Much more energy is released during the creation of new chemical bonds in
the products than is used in breaking the old bonds in the reactants.
 Energy Change in Chemical Processes
Endothermic Reactions:
Reactions in which energy flows from the surroundings into the system as the
reaction proceeds.

Much more energy is used for breaking the chemical bonds in the reactants
than it is released during the creation of the new bonds in the products.
Question 5: You strike a match and it burns.
a) Explain the energy transfers of this scenario using the terms
exothermic, endothermic, system, surrounding, chemical
potential energy, and kinetic energy in your discussion.
b) Sketch an energy level diagram for the process.
Substance on the tip of the match has chemical potential energy stored in its
chemical bonds. When friction increases the kinetic energy of the atoms
causing those bonds to break, the substance, which is the system, burns
releasing heat energy to the surrounding air. This process is exothermic because
more energy is released during combustion than it is absorbed during the
breaking of the initial bonds.

Question 6: Is the freezing of water an endothermic or exothermic process?

Explain.
The freezing process is exothermic because the water molecules have to lose
energy to the surroundings in order for them to change from a liquid state (high
internal kinetic energy!) to a solid state (lower kinetic energy!).
Question 7: Classify each process as exothermic or endothermic. Explain.
a) Your hand gets cold when you touch ice.
Exothermic because your hand loses thermal energy to the ice. Heat
energy always flow from the hot to the cold object.

b) The ice gets warmer when you touch it.

Endothermic because the ice is absorbing energy from your hand.
c) Water boils in a kettle being heated on a stove.
Endothermic because the water is absorbing energy from the material that
the kettle is made of.
d) Water vapor condenses on a cold pipe.
Exothermic because the water vapor is releasing energy to the pipe and
cooling off to the point at which vapor molecules change to a liquid state.
e) Ice cream melts.
Endothermic because the ice cream is absorbing energy from the
surrounding and the ice is changing into liquid state..
Question 8: For each of the following, define a system and its surroundings and
give the direction of energy transfer (exo- or endo-thermic).
a) Methane is burning in a Bunsen burner in a laboratory.
Methane is the system; air the surroundings; exothermic.

b) Water drops, sitting on your skin after swimming, evaporate.

Water is the system; skin is the surroundings; endothermic because liquid

water absorbs energy from your skin in order to change to vapor.

c) Two chemicals mixing in a beaker give off heat.

Chemicals is the system; beaker is the surroundings; exothermic because

the chemicals release heat to the beaker which gets warmer.
Question 9: Hydrogen gas and oxygen gas react violently to form water.
a)Which is lower in energy: a mixture of hydrogen and oxygen gases, or water?
b)Sketch an energy level diagram for this reaction.
Water is lower in energy because when hydrogen and
oxygen react, heat energy is released: exothermic process.

Question 10: Gas A2 reacts with gas B2 react to form gas AB. The bond energy
of AB is much greater than the bond energy of A2 or B2.
a)Is the formation of AB endothermic or exothermic?
b)Which is lower in energy, the reactants or the products?
Energy is absorbed to break the initial bonds and released when new bonds are
formed. If the bond energy of A-B is greater than the bond energy of A-A and
B-B, much more energy is released forming AB than absorbed to break the
bonds in A2 and B2  exothermic process.
In an exothermic process, the products (AB) are lower in energy.
 Ch. 6.2: Enthalpy of Reaction and Calorimetry
Enthalpy (H)

• H = E + PV

• System at constant pressure: ∆H = ∆E + P ∆V

• the heat at constant pressure qp can be calculated from:

• ∆E = qp + W = qp - P ∆V

• qp = ∆E + P ∆V  qp = ∆H

• ∆H = heat transfer to/from system at constant pressure

• Chemical Rxns.: ∆H = Hproducts – Hreactants

• Hproducts > Hreactants  +∆H  Endothermic rxn.

• Hproducts < Hreactants  -∆H  Exothermic rxn.

 Change in Enthalpy in Chemical Reactions
Problem 1: Methane (CH4) is burned at constant pressure, releasing 890 kJ/mol of
energy as heat.
a) Write the balanced thermochemical equation for the reaction.
b) Calculate the change in the enthalpy for a process in which 5.8g of methane is
burned at constant pressure.
(a) CH4 + 2O2  CO2 + 2H2O + 890 kJ/mol (H = -890 kJ/mol )
(b) Horxn = 5.8g CH4 1 mol -890 kJ = -321.8 ≈ -320 kJ
16.04 g 1 mol

Problem 2: The combustion of ethanol (C2H5OH) releases 1200 kJ/mol.

a) Write the balanced thermochemical equation for the reaction.
b) If we need to generate 6200 kJ of energy, how many grams of ethanol do we need
to burn?
(a) C2H5OH + 3O2  2CO2 + 3H2O + 1200 kJ/mol (H = -1200 kJ/mol )
(b) X grams C2H5OH = -6200 kJ 1 mol C2H5OH 46.07 g = 240 g C2H5OH
-1200 kJ 1 mol
 Calorimetry
• Calorimeter: Instrument used for measuring the amount of heat absorbed or
released during a physical change or chemical reaction.
• Substance releasing or absorbing the heat of reaction is usually water.
• Heat is determined by the change in temperature of a known quantity of
water
q = heat lost or gained [J]
q  s  m T s = specific heat capacity [J/g-ºC]
T = temperature change [[ºC]
• Specific heat capacity: amount of heat required to raise the
temperature of 1.0g of a substance by 1.0ºC [J/g-ºC]
• Heat of Reaction: ∆HRxn = - (qwater + qcalorimeter )
• qcalorimeter = Ccalorimeter ∙T
• Ccalorimeter : calorimeter heat capacity [J/ºC]

• Molar Heat of Reaction ∆H/mol = ∆HRxn / moles of reactant/product

Problem 3: The specific heat of graphite is 0.71 J/gºC. Calculate the energy
needed to raise the temperature of 75 kg of graphite from 294 K to 348 K.

Q = s m ∆T
Q = (0.71 J/g-ºC) (75 x103 g) (348 - 294) = 2875500 J = 2.9 x 106 J

Problem 4: A 46.2 g sample of copper is heated to 95.4ºC and then placed in a

calorimeter containing 75.0 g of water at 19.6ºC. The final temperature of both
the water and the copper is 21.8ºC. What is the specific heat of copper?
Water specific heat capacity is 4.184 J/g-ºC
(Hint: At final equilibrium temperature, all the heat energy lost by the metal
was absorbed by the water!)
- QCu lost = + Qwater gain
- (sCu mCu ∆TCu ) = + (swater mwater ∆Twater )
- (sCu) (46.2 g Cu) (21.8 – 95.4) = (4.184 J/g-ºC) (75.0 g water) (21.8 – 19.6)
- (sCu) (-3400.32) = 690.26  sCu = 0.203 J/g-ºC
Problem 5: For the equation: Na(s) + H2O(l)  NaOH(aq) + ½ H2(aq)
When 5.0 grams of sodium is placed into 100. mL of water, the temperature of
the solution increases by 7.0°C. Calculate ∆Hrxn/mol of Na.
Assume density and specific heat capacity of the solution to be same as water.

Hrxn = - Qwater = - (100 g) (4.184 J/g-ºC)(7.0 ºC) = -2929 J

# mol Na = 5.0 g / 22.99 g-mol-1 = 0.217 mol Na
Hrxn = -2929 J / 0.217 mol Na = -13.5 kJ/mol Na

Problem 6: For the equation: Ca(s) + 2HCl (aq)  CaCl2 (aq) + H2 (g)
If 2.0 grams of calcium is placed into 75 mL of 1.0M HCl solution at 18°C and
the final temperature of the system reaches 23°C, calculate ∆Hrxn/mole Ca.
Assume density and specific heat capacity of the solution to be same as water.

Hrxn = - Qwater = - (75 g)(4.184 J/g-ºC)(5ºC) = -1569 J

# mol Ca = 2.0 g / 40.08 g-mol-1 = 0.0499 mol Ca
Hrxn = -1569 J / 0.0499 mol Ca = -31.4 kJ/mol Ca
 Bomb Calorimetry
• Constant volume calorimeter is called a bomb
calorimeter.
• Material is put in a container with pure oxygen.
• Wires are used to start the combustion.
• The reaction container is put into a container of water.
• The heat capacity of the calorimeter is known and
tested.

Heat of Reaction: ∆HRxn = - (qwater + qcalorimeter )

qcalorimeter = Ccalorimeter ∙T

Ccalorimeter : heat capacity of the calorimeter [J/ºC]

Problem 7: You burn 0.300 g of C in an excess of O2 in a bomb calorimeter.
The temperature of the calorimeter which contains 775 grams of water
increases from 25°C to 27.38°C. The heat capacity of the calorimeter is 893
J/K. What is ∆Hrxn per mole of carbon?

Hrxn = - (qwater + qbomb) =

qwater = swater mwater ∆Twater & qbomb = Ccalorimeter Tbomb
qwater = (4.184 J/g-ºC)(775 g)(2.38 ºC) = 7717.39 J
qbomb = (893 J/K)(2.38 K)] = 2125.34 J
Qrxn = - (7717.39 + 2125.34) = -9842.73 = -9840 J = -9.84 kJ
# moles C = 0.300 g C *(1 mole/12.01 g) = 0.0250 moles C
Hrxn / mol C = -9.84 / 0.0250 = -394 kJ/mol C
Prbl.8: A 1.5886g sample of glucose (C6H12O6) was ignited in a bomb
calorimeter. The temperature increased by 3.682°C. The heat capacity of the
calorimeter was 3.562kJ/°C, and the calorimeter contained 1.000 kg of water.
Write the balanced thermochemical equation and find the molar heat of reaction
(i.e., kJ/mole of glucose).

(a) C6H12O6 + 6O2  6CO2 + 6H2O

(b) Hrxn = - (qwater + qbomb) =
qwater = swater mwater ∆Twater & qbomb = Ccalorimeter Tbomb
qwater = (4.184 J/g-ºC)(1000 g)(3.682 ºC) = 15405.49 J
qbomb = (3562 J/K)(3.682 K)] = 13115.28 J
Qrxn = - (15405.49 + 13115.28) = -28520.77 = -28520 J = -28.52 kJ
# moles C6H12O6 = 1.5886 g C6H12O6 *(1 mole/180.2 g) = 0.008816 mol C6H12O6
Hrxn / mol C6H12O6 = -28.52 / 0.008816 = -3235 kJ/mol C6H12O6
Problem 9: A 100.0 g sample of water at 90°C is added to a 100.0 g sample of
water at 10°C. The final temperature of the water is:
a) Between 50°C and 90°C b) 50°C c) Between 10°C and 50°C
Calculate the final temperature of the water.
- Qwater lost = + Qwater gain  - (swater mwater ∆Twater ) = + (swater mwater ∆Twater )
- (Tf – 90) = + (Tf – 10)
- Tf + 90 = Tf - 10  -2 Tf = -100  Tf = 50ºC

Problem 10: A 100.0 g sample of water at 90°C is added to a 500.0 g sample of

water at 10°C. The final temperature of the water is:
a) Between 50°C and 90°C b) 50°C c) Between 10°C and 50°C
Calculate the final temperature of the water.
- Qwater lost = + Qwater gain  - (swater mwater ∆Twater ) = + (swater mwater ∆Twater )
- (100.0) (Tf – 90) = + (500.0) (Tf – 10)
- 100.0 Tf + 9000 = 500.0 Tf - 5000  -600.0Tf = -14000  Tf = 23.3ºC
Problem 11: You have a Styrofoam cup with 50.0 g of water at 10C. You add a
50.0 g iron ball at 90C to the water. The final temperature of the water is:
a) Between 50°C and 90°C b) 50°C c) Between 10°C and 50°C
Calculate the final temperature of the water.
Specific heat of iron = 0.4456 J/g-ºC

- QFe lost = + Qwater gain  - (sFe mFe ∆TFe ) = + (swater mwater ∆Twater )
- (0.4456) (50.0 ) (Tf – 90) = (4.184) (50.0) (Tf – 10)
- 0.4456 Tf + 40.104 = 4.184 Tf - 41.84
- 4.630 Tf = -81.94  Tf = 17.7 ºC
 Ch. 6.3: Hess’s Law
• Enthalpy is a state function.
• Enthalpy of reaction does not depend on number of steps or pathway.
• From a particular set of reactants to a particular set of products, ∆HRxn is the
same whether the reaction takes place in one step or in a series of steps.
• We can add simpler, known reaction equations to come up with the desired
final equation.
• Two important rules:
a) If one step reaction is reversed the sign of ∆HRxn is also reversed.
b) If a step reaction is multiplied by a factor, so is ∆HRxn

N2 + 2O2  2NO2 ∆HRxn = ?

N2 + O2  2NO ∆HRxn = 180kJ

2NO + O2  2NO2 ∆HRxn = -112kJ
 Standard Enthalpy of Reaction (∆HºRxn )
• The ∆HRxn at standard conditions (25ºC, 1 atm , 1 M solutions)

Hess’s Law Problem 1: Given the following known reactions,

5
C2 H 2 (g) + O 2 (g)  2CO 2 (g) + H 2 O(l ) Hº  - 1300. kJ
2
C(s) + O2 (g)  CO2 (g) Hº  - 394 kJ

1
H 2 (g) + O 2 (g)  H 2 O (l) Hº  - 286 kJ
2

Find ∆HºRxn for the following reaction: 2C(s) + H 2 (g)  C2 H 2 (g)

2CO 2 (g) + H 2 O(l )  C 2 H 2 (g) + 5/2 O 2 (g) Hº   1300. kJ

2C(s) + 2O 2 (g)  2CO 2 (g) Hº  - 788 kJ

H 2 (g) + 1/2 O 2 (g)  H 2 O (l) Hº  - 286 kJ

2C(s) + H 2 (g)  C2 H 2 (g) ∆Ho = +226 kJ

Hess’s Law Problem 1: Given the following known reactions,
O2 (g) + H2 (g)  2OH(g) Hº   77.9kJ

O 2 (g)  2O(g) Hº   495 kJ

H 2 (g)  2H(g) Hº   435.9kJ

Find ∆HºRxn for the following reaction: O(g) + H(g)  OH(g)

1/2 O 2 (g) + 1/2 H 2 (g)  OH(g) Hº   38.95kJ

O(g)  1/2 O 2 (g) Hº  - 247.5 kJ

H(g)  1/2 H 2 (g) Hº   217.95kJ

O(g) + H(g)  OH(g) ∆Ho = -426.5 kJ

 Ch. 6.4: Standard Enthalpies of Formation (Hf)

 Hf of a compound: amount of heat needed for the formation of 1 mole of

a compound from its elements in their standard states.

• Standard state conditions are: 1 atm, 1M concentration and 25ºC

 Hf = 0 for all substances in their elemental states: H2(g), O2(g), N2(g),
Na(s), K(s), Fe(s), Al(s), etc.
Standard Enthalpy of Reaction (∆HºRxn )

∆HºRxn can be calculated from enthalpies of formation of each reactant and

product.
∆HºRxn = [np Hf(products)] – [nr Hf(reactants)]
Problem 1: For each of the substances below, write a balanced equation
showing the formation of 1 mole of the compound from its elements in their
standard states. Look up the value for Hf in the Appendix of the textbook.
a)Al2O3

b) Mg(OH)2

c) C12H22O11

d) NaHCO3
Problem 2: Use the standard enthalpy of formation of the compounds to
calculate the standard heat of reaction (∆HºRxn ):
C2H5OH (l) + 3O2 (g)  2CO2 (g) + 3H2O (g)

Problem 3: Nitroglycerin is a powerful explosive that decomposes by the

following equation while giving off 4200 kJ of heat.
C3H5(NO3)3  3/2N2 (g) + ¼O2 (g) + 3CO2 (g) + 5/2H2O (g)
Calculate the Hf of nitroglycerin.
 Hess’s Law & Standard Enthalpy of Formation (Hf)
Using the following data, calculate the heat of formation of the
compound ICl (g) from its elements at 25°C.
H° (kJ/mol)
Cl2 (g)  2Cl (g) 242.3
I2 (g)  2I (g) 151.0
ICl (g)  I (g) + Cl (g) 211.3
I2 (s)  I2 (g) 62.8
 Bond Energies and Enthalpy of Reaction (∆HRxn )
• Using published value of atomic bond energies, we can find the change in the
enthalpy for a reaction.
• In order to break existing bonds, energy must be added to the compounds.
• When new bonds are formed, energy is released to the surrounding.
• If we add up all the energy it took to break the bonds, and subtract all the
energy released forming the bonds we get the ∆HRxn.

∆HRxn = [ D(bonds broken)] – [ D(bonds formed)]

D: bond energy/mole [kJ/mol]

 Bond Energies and Enthalpy of Reaction (∆HRxn )
Problem 1: The bond energy (kJ) for H-H, F-F, and H-F are 432, 154 and 565
kJ/mol respectively, calculate the enthalpy of the reaction: H2 + F2  2HF

Problem 2: Calculate the heat of reaction (∆HRxn) for: 2H2 + O2  2H2O

Bond energies: H-H: 432 kJ/mol, O ═ O: 495 kJ/mol, O-H: 467 kJ/mol
 Bond Energies and Enthalpy of Reaction (∆HRxn )
Problem 3: Calculate the enthalpy of reaction (∆HRxn):
CH4 + 3Cl2 CHCl3 + 3HCl
Bond energies: C-H: 413 kJ/mol, Cl-Cl: 239 kJ/mol, C-Cl: 339 kJ/mol,
H-Cl: 427 kJ/mol

Problem 4: Calculate ∆HRxn for the following reaction given the bond energies
below: C2H4 + H2  C2H6
Bond energies: C=C: 614 kJ/mol, C-H: 413 kJ/mol, H-H: 432 kJ/mol,
C-C: 347 kJ/mol
Use the value of the bond energies to find the energy for this reaction:
Is this an endothermic or exothermic reaction?