Thermochemistry

Chapter 6

Energy
Energy is defined as the capacity to do work or produce heat. The Law of Conservation of Energy states that energy can be neither created or destroyed it can only change form.
Therefore, the energy of the universe is constant.

Potential or Kinetic?
Energy can be classified as either potential or kinetic. Potential energy is stored energy resulting from an objects position or composition.
Potential energy due to position results from gravity. Potential energy due to composition results from attractive forces between atoms (bonds).

Kinetic Energy is the energy of motion.

K.E. = mv2 where m=mass and v=velocity

Heat vs Temperature
Temperature is a property that reflects the random motion of the particles in a substance. It is a measure of the avg. kinetic energy of the particles. Heat involves the transfer of energy between two objects due to a temperature difference.

Work
Work is defined as force acting over a distance. There are 2 ways to transfer energy:
Through Work Through Heat

The way that energy transfer is divided between work and heat is dependent upon the specific conditions, called the pathway.

 The total energy transferred is constant regardless of the pathway.

The amounts of work and heat, however, will differ.

Energy change is independent of the pathway; however, work and heat are both dependent on the pathway. A state function refers to a property of the system that depends only on its present state. It does NOT depend in any way on the systems past or future. A change in a state function is independent of the pathway taken between the two states.
Energy is a state function, work and heat are NOT.

Chemical Energy
Consider the combustion of methane which is used to heat many homes.
CH4(g) + 2O2(g) CO2(g) + 2H2O(g) + energy (heat)

To discuss this reaction we divide the universe into 2 parts: the system and the surroundings.
The system is the part of the universe on which we wish to focus attention. The surroundings include everything else in the universe.

In the above example we would define the system as the reactants and products of the reaction. The surroundings consists of everything else.

Exothermic vs Endothermic
When a reaction results in the evolution of heat, it is said to be exothermic; that is, energy flows out of the system.
In the combustion of methane energy flows out of the system as heat.

When a reaction absorbs energy from the surroundings it is said to be endothermic; that is, energy flows into the system.

 Where does the energy, released as heat, come from in an exothermic reaction? Since energy must be conserved we know that the energy gained by the surroundings must be equal to the energy lost by the system. In the combustion of methane, the energy content of the system decreases, which means that 1 mole of CO2 and 2 moles of H2O (the products) possess less potential energy than do 1 mole of CH4 and 2 moles of O2 (the reactants). In any exothermic reaction, some of the potential energy stored in the chemical bonds is being converted to thermal energy via heat. For exothermic rxns: the P.E. of the products is less than the P.E. of the reactants. In any endothermic reaction, the situation is reversed. Energy that flows into the system is used to increase the potential energy of the system. For endothermic rxns: the P.E. of the products is greater than the P.E. of the reactants.

Combustion of Methane

 PE
PE represents the change in potential energy stored in the bonds of the products as compared with the bonds of the reactants. Energy is required or absorbed when bonds are broken. Energy is released when new bonds are formed. In exothermic reactions more energy is released by forming the new bonds in the products than is used to break the bonds in the reactants. Thus, the surplus energy is released to the surroundings as heat. In endothermic reactions more energy is used to break the bonds in the reactants than is released by forming the new bonds in the products. Thus, energy must be absorbed from the surroundings.

Endothermic Reaction

Thermodynamics
The study of energy and its interconversions is called thermodynamics. The Law of Conservation of Energy is often called the First Law of Thermodynamics and is stated as follows: The energy of the universe is constant. The internal energy E of a system can be defined as the sum of the kinetic and potential energies of all the particles in the system. The internal energy of a system can be changed by a flow of work, heat, or both. E = q + w Where E represents the change in internal energy, q represents heat, and w represents work.

 Thermodynamic quantities always consist of a number and a sign, indicating the direction of flow. The sign reflects the systems point of view. If energy flows into the system via heat (endothermic reaction), q is assigned a positive sign. When energy flows out of the system (exothermic reaction), q is assigned a negative sign. E is always positive for endothermic rxns. E is always negative for exothermic rxns.

 The same conventions apply to the flow of work. If the system does work on the surroundings (energy flows out of the system), w is negative. If the surroundings do work on the system (energy flows into the system), w is positive.

Sample Problem #1
Calculate E 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. We use the equation: E = q + w q = +15.6 kJ, since the process is endothermic W = +1.4 kJ, since work is done on the system. E = 15.6 kJ + 1.4 kJ = 17.0 kJ The system has gained 17.0 kJ of energy.

Work Applied to Gases

A common type of work associated with chemical processes is work done by a gas (through expansion) or work done to a gas (through compression). Work = -Pressure x Change in Volume or w = -PV For a gas expanding against an external pressure, w is a negative quantity since work flows out of the system. For a gas being compressed by an external pressure, w is a positive quantity since work flows into the system.

Sample Problem #2
Calculate the work associated with the expansion of a gas from 46 L to 64 L at a constant external pressure of 15 atm. w = -PV w = -(15 atm) x (64 L 46 L) w = -270 L atm

Sample Problem #3
A balloon is being inflated to its full extent by heating the air inside it. In the final stages of this process, the volume of the balloon changes from 4.00 x 106 L to 4.50 x 106 L by the addition of 1.3 x 108 J of energy as heat. Assuming that the balloon expands against a constant pressure of 1.0 atm, calculate E for the process. (To Convert between L atm and J, use 1 L atm = 101.3 J)

Sample Problem # 3 - Solution

We use the equation: E = q + w Since the problem states that 1.3 x 108 J of energy is added as heat, q = 1.3 x 108 J The work can then be calculated from: w = -P V w = -(1.0 atm) x (4.50 x 106 L - 4.00 x 106 L) w = -5.0 x 105 L atm To calculate E, we must sum q and w. Since the units are not the same we must change the unit of work to J.

Sample Problem #3 (Solution cont.)

w = -5.0 x 105 L atm w = -5.0 x 105 L atm x

101.3 J 1 L atm

W = -5.1 x 107 J E = q + w E = (+1.3 x 108 J) + (-5.1 x 107 J) E = 8 x 107 J

Enthalpy
Enthalpy, H, is defined as: H = E + PV Where E is the internal energy of the system, P is the pressure of the system, and V is the volume of the system. Enthalpy is a state function. For a process carried out at constant pressure and where the only work allowed is that from a volume change, we can say that the change in enthalpy of the system is equal to the energy flow as heat: H = q

For this reason, the terms heat of reaction and change in enthalpy are used interchangeably for reactions studied at constant pressure. For a chemical reaction, the enthalpy change is given by the equation: H = H products - H reactants

In a case in which the reactants of a reaction have a greater enthalpy than the products, H will be negative. The overall decrease in enthalpy is achieved by the generation of heat which has flowed out of the system and the reaction is exothermic. In a case in which the products of a reaction have a greater enthalpy than the reactants, H will be positive. Thus, heat has been absorbed by the system and the reaction is endothermic.

Sample Problem #4
When 1 mole of methane (CH4) is burned at constant pressure, 890 kJ of energy is released as heat. Calculate H for a process in which a 5.8 g sample of methane is burned at constant pressure.

Sample Problem #4 Solution

5.8 g CH4 x 1 mol CH4 x 16.0 g CH4 -890 kJ 1 mol CH4 =

H = -320 kJ

Calorimetry
The instrument used to determine the heat associated with a chemical reaction is called a calorimeter. Substances respond differently to being heated. The heat capacity, Cp, of a substance is defined as Cp = heat absorbed = H increase in temperature T

Specific Heat Capacity

When heat capacity is given per gram of substance it is called the specific heat capacity and its units are J/C g

Constant Pressure Calorimetry

The measurement of heat using a simple calorimeter. Pressure remains constant. Used to determine changes in enthalpy for reactions occurring in solution.

Calorimetry Calculations
Energy released by the reaction = Energy absorbed the solution = mass of solution (m) x specific heat capacity (c) x change in temp. (T) q = m x c x T The specific heat capacity of water is 4.18 J/C g and is used for calculations involving aqueous solutions.

Calorimetry Calculation #1
When 1.00 L of 1.00 M Ba(NO3)2 solution at 25 C is mixed with 1.00 L of 1.00 M Na2SO4 solution at 25 C in a calorimeter, the white solid BaSO4 forms and the temperature of the mixture increases to 28.1 C. Assume that the specific heat of solution is 4.18 J/C g and the density of solution is 1.0 g/mL. Calculate the enthalpy change per mole of BaSO4 formed.

Ba(NO3)2 + Na2SO4 BaSO4 + 2NaNO3 Sodium and nitrate are spectator ions so the net ionic equation is Ba2+(aq) + SO4-(aq) BaSO4(s) We use the equation: q = m x c x T We first need to find the mass of solution The total volume of solution is 2.0 L, so 2.0 L x 1000 mL x 1.0 g = 2.0 x 103 g 1L 1 mL q = (2.0 x 103 g) x (4.18 J/C g) x (28.1C-25.0C) q = -2.6 x 104 J Since, 1.0 L of 1.0M barium nitrate contains 1.0 mol of Ba2+, and 1.0L of 1.0M sodium sulfate contains 1.0 mol of SO42-, 1.0 mol of BaSO4 is formed. Therefore H = -2.6 x 104 J/mol or -26 kJ/mol

Calorimetry Calculation #2
A 110. g sample of copper (specific heat capacity = 0.20 J/C g) is heated to 82.4 C and then placed in a container of water at 22.3 C. The final temp. of the water and metal is 24.9 C. What is the mass of the water in the container assuming all heat was transferred from the metal to the water?

Heat In = Heat Out

Heat lost by copper = Heat gained by water q(Cu) = qH2O m x c x T = m x c x T
(110. g) x (0.20 J/C g) x (57.5C) = (m) x (4.18 J/C g) x(2.6C)

116 g = mass of water

Constant Volume Calorimetry

Energy changes in reactions at constant volume are performed in a bomb calorimeter. Energy change is determined by measuring the increase in the temp. of the water and other calorimeter parts.

Calorimetry Calculation #3
A 0.1964 g sample of quinone (C6H4O2) is burned in a bomb calorimeter that has a heat capacity of 1.56 kJ/C. The temperature of the calorimeter increases by 3.2 C. Calculate the energy of combustion of quinone per gram and per mole.

In a bomb calorimeter q = (heat capacity) x (change in temp) so q = (1.56 kJ/C) x (3.2 C) q = 5.0 kJ = energy of combustion 5.0 kJ / 0.1964 g = 25 kJ/g 25 kJ x 108 g = 2700 kJ/mol 1g 1 mol

Hesss Law
When going from a particular set of reactants to a particular set of products, the change in enthalpy is the same whether the reaction takes place in one step or multiple steps. When using Hesss Law its important to note:
If a reaction is reversed the sign of H is reversed. The magnitude of H is directly proportional to the quantities of reactants and products. If the coefficients in a balanced rxn are multiplied by an integer, the value of H is multiplied by the same integer.

Hints for Hesss Law

Calculations involving Hesss Law typically require that several reactions be manipulated and combined to finally give the reaction of interest. It is often easiest to work backwards from the required reaction using the reactants and products to determine how to manipulate the other reactions at your disposal. Reverse any reactions as needed and multiply those reactions by an integer if necessary to get the required amounts.

Standard Enthalpy of Formation

The standard enthalpy of formation (Hf) of a compound is defined as the change in enthalpy that accompanies the formation of one mole of a compound from its elements with all substances in their standard states.

Definitions of Standard State

For a Compound
The standard state of a gaseous substance is a pressure of 1 atm. For a pure substance in a condensed state, the standard state is the pure liquid or solid. For a substance present in solution, the standard state is a concentration of exactly 1M.

For an Element
The standard state for an element is the form in which the element exists under conditions of 1 atm and 25C