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Chapter 6 Thermochemistry Thermochemistry is a branch of thermodynamics and is the study of heat changes in chemical reactions.

6.2 The Nature of Energy: Key Definitions (p. 215)

Energy (E) can be defined as the capacity to do work. Two fundamental classifications of energy are:

1. Kinetic energy (E k ) =

2. Potential energy (E p ) =

The SI unit of energy is a derived unit called the joule (J).

1 J = 1 kg·m 2 /s 2

1 calorie (cal) =

1 food calorie (Cal) =

Problem #1 How many joules are in a can of Dr. Pepper © (150 Cal)?

6.3 The First Law of Thermodynamics (p. 216)

The total energy of the

is

Internal energy (E) is the

of

the

and

energies of a

The universe is understood to be divided into two separate but integral parts, the

and the

The system is the substance or mixture of substances under study in which a change occurs or simply stated, it is the part of the universe under investigation. The surroundings compose the other part of the universe. In other words, the surroundings include both the apparatus which contains the substance under study, and the space around the apparatus. Separating the system from the surroundings is the boundary, which can be real (like the walls of a beaker) or imaginary.

E system = E final - E initial

E system = E products - E reactants

Stated mathematically in terms of internal energy (E), heat (q), and work (w), the law of conservation of energy is referred to as the first law of thermodynamics and is expressed as:

ΔE system =

+

All thermodynamic quantities have a

and a

Heat (q) “flows” spontaneously from the

object to the

object.

-q

System

heat

+q

System

heat

-w

System

work

+w

System

work

Internal Energy Problem #1 A gas absorbs 35.0 J of heat and does 15.0 J of work. What is ΔE?

Internal Energy Problem #2 Which of the following would result in a decrease of 35.0 J in the internal energy of a system?

a. A system gains 40.0 J of heat and has 75.0 J of work done on it.

b. A system loses 40.0 J of heat and has 75.0 J of work done on it.

c. A system loses 40.0 J of heat and does 75.0 J of work.

d. A system gains 40.0 J of heat and does 75.0 J of work.

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6.4 Quantifying Heat and Work: Specific Heat Capacity and Specific Heat (p. 221)

Heat spontaneously flows from higher temperature to lower temperature. Calorimetery is the science of measuring the heat change associated with either a physical or

chemical process.

object is heated, its temperature increases and when the object cools, its temperature decreases.

When a system absorbs heat its temperature changes, provided that no physical change takes place (phase change) and no reaction occurs. When an

Heat capacity (C) is the amount of heat (q) required to raise the temperature of an object (system) one degree Celsius. The heat change of a system is described by the mathematical relationship:

q =

The units for heat capacity are J/ o C.

The change in temperature (ΔT) of the object is defined as: ΔT = T final - T initial

Heat Capacity Problem #1 How much heat is required to raise the temperature of an object from 25.00 o C to 60.00 o C, if the heat capacity of the object is 0.755 J/ o C?

Heat Capacity Problem #2 An object with a heat capacity of 38.25 J/ o C lost 4.593 kJ of heat. If the initial temperature was 235.19 o C, calculate the final temperature after the cooling process.

The specific heat capacity, C s , (or specific heat) is the amount of heat required to raise the temperature of one gram of a substance one degree Celsius or Kelvin.

Specific heat is an intensive property but varies with temperature.

The mathematical equation relating specific heat and temperature change is:

q =

Specific Heat Capacity Problem #1 What amount of heat is released when a 100.0 gram sample of copper cools from 95.00°C to 65.00°C?

The specific heat capacity of copper is 0.382 J/g·°C.

Specific Heat Problem #2 If the original temperature of a 20.00 g sample of iron is 25.00 o C, calculate the final temperature of the iron if 300.00 J of heat is removed from it. The specific heat of iron is 0.4494 J/go C.

Specific Heat Problem #3 Calculate the final temperature when 25.00 g of water at 20.0 o C is mixed with 75.00 g of water at 40.00 o C.

Work: Pressure-Volume Work (p. 225)

w =

g of water at 20.0 o C is mixed with 75.00 g of water at 40.00

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Pressure-Volume Work Problem #1A Calculate the work for the expansion of a gas from 50.0 L to 75.0 L at 1.00 atm.

Pressure-Volume Work Problem #1B

Convert this value to joules.

1 L·atm = 101.325 J

6.5 Measuring E for Chemical Reactions: Constant-Volume Calorimetery (p. 227)

The heat associated with a reaction carried out at constant volume conditions (q v ) is equivalent to ΔE rxn .

E rxn = q v = q rxn

A bomb calorimeter (combustion calorimeter) is a device used to measure ΔE rxn for a combustion reaction.

combustion chamber (the bomb) wherein the reaction takes place, set in another chamber filled with water surrounding the bomb. Heat generated by combustion is

transmitted to the bomb and then to the water, raising temperature of both. = (C cal )(T)

Combustion calorimeters are usually composed of a

The heat transmitted to the calorimeter can be calculated from the following equation: q cal

The heat absorbed by the calorimeter is equal in magnitude but opposite in sign to the heat generated by the reaction.

q cal

= -q rxn

Bomb Calorimeter Problem #1 When a 3.500 g sample of graphite was burned to CO 2 in a bomb calorimeter, the temperature of the calorimeter rose from 25.00 o C to 38.18 o C. Calculate ΔE rxn for the combustion of carbon in kilojoules per gram. The heat capacity of the calorimeter is 8.952 kJ/ o C.

Bomb Calorimeter Problem #2

A 1.435 g sample of naphthalene (C 10 H 8 ) was burned in a constant-volume bomb calorimeter. Consequently, the temperature of the calorimeter rose from 20.00 o C to

30.72 o C. The heat capacity of the calorimeter is was 5.38 kJ/ o C. Use this data to calculate the ΔE rxn for the combustion of naphthalene in kJ/mol.

naphthalene is 128.18 g/mol.

The molar mass of

6.6 Enthalpy: The Heat Evolved in a Chemical Reaction at Constant Pressure (p. 229)

Enthalpy (H) the heat transferred in a physical or chemical process occurring at constant pressure (q p ).

H is an endothermic process and heat flows into the system. In other words, in an endothermic process, heat flows into the system. Heat + H 2 O(l) H 2 O(g)

-ΔH is an exothermic process and heat flows out of the system. CH 4 (g) + 2 O 2 (g) CO 2 (g) + 2 H 2 O(g) + heat

In other words, in an exothermic process, heat flows out of the system.

6.6 Thermochemical Equations

A thermochemical equation (p. 232) is a balanced chemical reaction equation (including phase labels) with the enthalpy of reaction value written directly after the

equation.

N 2(g) + O 2(g) 2 NO (g)

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

ΔH = +182.6 kJ/mol

ΔH = -110.53 kJ

Thermochemical Equation Problem #1 Using the following thermochemical equation, calculate how much heat is associated with the synthesis of 4.00 moles of NH 4 Cl.

NH 3 (g) + HCl(g) NH 4 Cl(s)

H = -176 kJ

Thermochemical Equation Problem #2 How much energy is associated with the combustion of 22.50 g of CH 4 ?

CH 4(g) + 2O 2(g)

CO 2(g) + 2H 2 O (l)

ΔH = -890 kJ

Thermochemical Equation Problem #3 Calculate the mass of ethane, C 2 H 6 , which must be burned to produce 100 kJ of heat.

2C 2 H 6 (g) + 7O 2 (g) 4CO 2 (g) + 6H 2 O(l)

ΔH = -3120 kJ

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