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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 object’s 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. = ½ 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.

• 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. .Work • Work is defined as force acting over a distance.

will differ. • A change in a state function is independent of the pathway taken between the two states. • Energy change is independent of the pathway. however. – The amounts of work and heat. • 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 system’s past or future. work and heat are NOT. . – Energy is a state function.• The total energy transferred is constant regardless of the pathway. however. work and heat are both dependent on the pathway.

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– The surroundings include everything else in the universe.Chemical Energy • Consider the combustion of methane which is used to heat many homes. The surroundings consists of everything else. • In the above example we would define the system as the reactants and products of the reaction. – The system is the part of the universe on which we wish to focus attention. 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. .

• When a reaction absorbs energy from the surroundings it is said to be endothermic. – In the combustion of methane energy flows out of the system as heat. it is said to be exothermic.Exothermic vs Endothermic • When a reaction results in the evolution of heat. that is. energy flows into the system. energy flows out of the system. that is. .

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. • For endothermic rxns: the P.• Where does the energy. • In the combustion of methane.E. of the products is greater than the P. the situation is reversed. 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). • For exothermic rxns: the P.E.E. of the reactants. • In any exothermic reaction. the energy content of the system decreases. • In any endothermic reaction. of the products is less than the P. . some of the potential energy stored in the chemical bonds is being converted to thermal energy via heat.E. released as heat. of the reactants. Energy that flows into the system is used to increase the potential energy of the system.

Combustion of Methane .

energy must be absorbed from the surroundings. • 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. • Energy is required or absorbed when bonds are broken. .∆ PE • ∆ PE represents the change in potential energy stored in the bonds of the products as compared with the bonds of the reactants. • 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. • Energy is released when new bonds are formed. – Thus.

Endothermic Reaction .

• 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.Thermodynamics • The study of energy and its interconversions is called thermodynamics. • The internal energy of a system can be changed by a flow of work. and w represents work. or both. heat. ∆E = q + w Where ∆E represents the change in internal energy. . q represents heat.

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

• If the surroundings do work on the system (energy flows into the system).• 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. w is positive.

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4 kJ. since work is done on the system.6 kJ of heat flows and where 1. . ∆E = 15.0 kJ The system has gained 17. We use the equation: ∆E = q + w q = +15. since the process is endothermic W = +1.4 kJ = 17.Sample Problem #1 • Calculate ∆E for a system undergoing an endothermic process in which 15.6 kJ.4 kJ of work is done on the system.0 kJ of energy.6 kJ + 1.

. w is a positive quantity since work flows into the system. Work = -Pressure x Change in Volume or w = -P∆V For a gas expanding against an external pressure.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). For a gas being compressed by an external pressure. w is a negative quantity since work flows out of 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 = -P∆V w = -(15 atm) x (64 L – 46 L) w = -270 L ∙ atm .

50 x 106 L by the addition of 1. use 1 L ∙ atm = 101. In the final stages of this process.0 atm.Sample Problem #3 • A balloon is being inflated to its full extent by heating the air inside it.00 x 106 L to 4. calculate ∆E for the process. Assuming that the balloon expands against a constant pressure of 1.3 J) . (To Convert between L ∙ atm and J.3 x 108 J of energy as heat. the volume of the balloon changes from 4.

00 x 106 L) w = -5.4.Solution We use the equation: ∆E = q + w Since the problem states that 1. we must sum q and w. q = 1. Since the units are not the same we must change the unit of work to J. .0 x 105 L ∙ atm To calculate ∆E.3 x 108 J of energy is added as heat.50 x 106 L .Sample Problem # 3 .3 x 108 J The work can then be calculated from: w = -P ∆V w = -(1.0 atm) x (4.

3 J 1 L ∙ atm W = -5.) w = -5.1 x 107 J) ∆E = 8 x 107 J .1 x 107 J ∆E = q + w ∆E = (+1.3 x 108 J) + (-5.Sample Problem #3 (Solution cont.0 x 105 L ∙ atm x 101.0 x 105 L ∙ atm w = -5.

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

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

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

Calculate ∆H for a process in which a 5. .Sample Problem #4 • When 1 mole of methane (CH4) is burned at constant pressure.8 g sample of methane is burned at constant pressure. 890 kJ of energy is released as heat.

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. of a substance is defined as Cp = heat absorbed = ∆H increase in temperature ∆T . • Substances respond differently to being heated. Cp. • The heat capacity.

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. • Used to determine changes in enthalpy for reactions occurring in solution. . • Pressure remains constant.

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.

the white solid BaSO4 forms and the temperature of the mixture increases to 28.Calorimetry Calculation #1 • When 1. .18 J/C ∙ g and the density of solution is 1.00 L of 1. Calculate the enthalpy change per mole of BaSO4 formed.0 g/mL.00 M Ba(NO3)2 solution at 25 C is mixed with 1.00 M Na2SO4 solution at 25 C in a calorimeter. Assume that the specific heat of solution is 4.00 L of 1.1 C.

0L of 1.0 mol of SO42-.0 mol of BaSO4 is formed. and 1.0 x 103 g 1L 1 mL q = (2.0 L. Therefore… ∆H = -2.0 L of 1.0C) q = -2.0 mol of Ba2+.6 x 104 J/mol or -26 kJ/mol .0 L x 1000 mL x 1.0M barium nitrate contains 1. so… 2.0 g = 2.1C-25. 1.0 x 103 g) x (4.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 2.6 x 104 J Since.0M sodium sulfate contains 1.18 J/C ∙ g) x (28. 1.

g sample of copper (specific heat capacity = 0.4 C and then placed in a container of water at 22.3 C.20 J/C ∙ g) is heated to 82.9 C. What is the mass of the water in the container assuming all heat was transferred from the metal to the water? . The final temp. of the water and metal is 24.Calorimetry Calculation #2 A 110.

20 J/C ∙ g) x (57.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 (0.18 J/C ∙ g) x(2.6C) 116 g = mass of water .5C) = (m) x (4.

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

The temperature of the calorimeter increases by 3. Calculate the energy of combustion of quinone per gram and per mole.1964 g sample of quinone (C6H4O2) is burned in a bomb calorimeter that has a heat capacity of 1.2 C.56 kJ/C. .Calorimetry Calculation #3 A 0.

0 kJ = energy of combustion 5.1964 g = 25 kJ/g 25 kJ x 108 g = 2700 kJ/mol 1g 1 mol .0 kJ / 0.56 kJ/C) x (3.2 C) q = 5.In a bomb calorimeter… q = (heat capacity) x (change in temp) so… q = (1.

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

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• 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. .Hint’s for Hess’s Law • Calculations involving Hess’s Law typically require that several reactions be manipulated and combined to finally give the reaction of interest.

Standard Enthalpy of Formation • The standard enthalpy of formation (∆Hf⁰) 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. .

– For a pure substance in a condensed state. • For an Element – The standard state for an element is the form in which the element exists under conditions of 1 atm and 25C . the standard state is the pure liquid or solid. – For a substance present in solution.Definitions of Standard State • For a Compound – The standard state of a gaseous substance is a pressure of 1 atm. the standard state is a concentration of exactly 1M.