Thermochemistry 6.1 The Nature of Energy Energy is usually defined as the capacity to do work.

Chemist define work as directed energy change resulting from a process. There are many forms of energy and they are intercovertible. Example : radiant energy, thermal energy, chemical energy and potential energy. Law of conservation of energy : the total quantity of energy in the universe is assumed constant. 6.2 Energy Change in Chemical Reactions heat = transfer of thermal energy between two bodies that are at different temperatures. thermochemistry = the study of heat change in chemical reactions. System = the specific part of the universe that is of interest to us. open system = can exchange mass and energy. close system = allows the transfer of energy (heat) but not mass. isolated system = does not allow the transfer of either mass or energy. exothermic process = any process thats gives off heat - transfers thermal energy to the surrondings. endothermic process = heat has to be supplied to the system by the surrondings.

Open System

Close System Isolated System

6.3

Enthalpy

The heat flow into or out of a system in a constant pressure process. H, change in enthalpy / enthalpy of reaction is the different between the enthalpies of the products and the enthalpies of the reactants : H = H (products) - H (reactants) H (positive) = endothermic process H (negative) = exothermic process 2H2 (g) + O2 (g) 2H2O (l) H = - X kJ

Thermochemical equations = show the enthalpy changes as well as the mass relationships. the stoichiometric coefficients refer to the number of moles of a substances. reverse equation, magnitude of H remain the same but its sign changes. multiply both side of a thermochemical equation by a factor n, H also change by the same factor . thermochemical equations must specify the physical state of all reactant and products. 6.4 Calorimetry

Calorimetry, the measurement of heat changes. The specific heat (s) of a substance is the amount of heat required to raise the temperature of one gram of the substance by one degree Celsius. The heat capacity ( C ) of a substance is the amount of heat required to raise the temperature of a given quantity of the substance by one degree Celcius.
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Heat capacity , C = ms Enthalpy change, q = ms t = C t Constant-Volume Calorimetry

t = t final - t initial

Bomb Calorimeter isolated system (combustion reactions) q system = q water + q bomb + q rxn =0 q rxn = - ( q water + q bomb) q water = m s t q water = m water (4.18 J/gC) t q bomb = C bomb t Constant-Pressure Calorimeter non-combustion reactions = q soln + q calorimeter + q rxn =0 q rxn = - ( q soln + q calorimeter ) q soln = m soln S soln t ( assume : S soln = 4.184 J / g C ) q calorimeter = C calorimeter t 6.5 Standard Enthalpy of Formation and Reaction Standard Enthalpy of formation = heat change that results when one mole of a compound is formed form its elements at a pressure of 1 atm ( Hf ) (See table 6.3) . Standard Enthalpy of reaction; the enthalpy of reaction carried out at 1 atm. AA + bB cC + dD
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q system

H rxn = [cHf ( C ) + dHf (D) ] [aHf (A) + bHf (B) ] H rxn = n Hf (product) nHf (reactants)

There are two methods to identify H f / H rxn :

a)

direct method : C + O2 (g)

CO2 (g) Hrxn = -393.5 kJ CH4 (g)

b)

indirect method : C (graphite) + 2 H2 (g)

* Hesss Law when reactants are converted to products, the change in enthalpy is same whether the reaction take place in one step or a series of steps. 6.6 Standard Enthalpy of Formation and Reaction Heat of solution or enthalpy of dilution, Hsoln is the heat generated or absorbed when a certain amount of solute dissolves in a certain amount of solvent. H soln = H solvent H components Example : NaCl(s) Step 1 : solid state Step 2 : gaseous state Na + (g) + Cl- (g)
Lattice energy (+ve )

Hsoln = ?

ionics gaseous state

Heat of hydration (-ve)

hydrated ions

Heat of dilution = the heat change associated with the dilution process, (exothermic, endothermic).

6.7 Thermodynamics-Thermochemistry Thermochemistry is a part of thermodynamics, which is the scientific study of interconversion of heat and other kinds of energy. We study about the state of the system and state functions. 1st Law of Thermodynamics ; Energy can be converted from one form to another but cannot be created or destroyed. E = Ef Ei E sys + E surr = 0 Esys = - Esurr E=q+w Process Sign Work done by the system to the surrounding (w) Work done on the system by the surrounding (w) + Heat absorbed by the system from the surrounding (q) + Heat absorbed by the surrounding from the system (q) Work , Heat and Enthalpy E = q + w If P is constant : q = H, w = - PV E = H PV H = E + PV

If assume as ideal gas behavior and constant temperature : E = H RTn H = E + RTn V = V final V initial n = no. of moles of product gases no. of moles of reactant gases.