CALORIMETRY ΔH of a chemical rxn can experimentally be determined by measuring the heat flow accompanying the rxn at constant pressure. When heat flows into/out of a substance, its temperature changes. The heat flow is experimentally determined by using the temperature change produced.

The measurement of heat flow is called “calorimetry” and the apparatus used to measure the heat flow is called “a calorimeter.” CALORIMETRY

Heat capacity (C or m.c) of an object is the amount of heat required to raise its temperature by 1 K or 1 °C. The greater the heat capacity, the greater the heat required to produce a certain rise in temperature. CALORIMETRY

Specific heat capacity or specific heat (s or c) is the heat capacity of 1 g of a substance.  Specific heat of H2O(l) is the amount of energy required to change temperature of 1 g of water by 1°C. Therefore, it is J/g-K or 1 cal/g –K. CALORIMETRY

substanceSpecific heat ( J/g-K) N2 (g)1.04 Al(s).90 Fe(s).45 H2O(l)4.18 Specific heat of water is quite higher than those of other substances. It’s very important for Earth’s climate since it makes oceans resistant to temperature changes.

The amount of heat gained /lost by a substance: CALORIMETRY q=(grams of substance)x(specific heat)x ΔT Q=mcΔT !!!ΔT in K = ΔT in °C

When a substance gains heat - its temperature rises. When a substance loses heat, - Its temperature lowers. CALORIMETRY

CALORIMETERS 1) CONSTANT-PRESSURE CALORIMETER - A coffee-cup calorimeter - Because the calorimeter isn’t sealed, the rxn happens under constant pressure of the atmosphere.

CALORIMETERS 1) CONSTANT-PRESSURE CALORIMETER - Since the calorimeter has a very low thermal conductivity & heat capacity, we assume that; 1. The heat absorbed/gained during the rxn doesn’t escape the coffee cup. 2. The calorimeter itself doesn’t absorb/release heat.

Coffee cup calorimeter is usually used to determine the “heat of solution” and “heat of neutralization.” CALORIMETERS 1) CONSTANT-PRESSURE CALORIMETER

- Heat exchange happens only between the solution and the chemicals reacting in the calorimeter. Therefore; In exothermic rxns: q lost by the rxn = - q gained by the solution In endothermic rxns: q gained by the rxn = - q lost by the solution - q solution = -(specific heat of solution)x(grams of soln)xΔT=q rxn

CALORIMETERS 1) CONSTANT-PRESSURE CALORIMETER q rxn = - q solution ΔH rxn = q rxn / (number of moles of the acid/base reacted ) ΔH rxn = q rxn / (number of moles of the solid dissolved )

For dilute aqueous solutions, the specific heat of solution will be approximately the same as that of water. CALORIMETERS 1) CONSTANT-PRESSURE CALORIMETER

Example 1 When a student mixes 50. mL of 1.0 M HCl and 50. mL of 1.0 M NaOH in a coffee-cup calorimeter, the temperature of the resultant solution increases from 21.0 °C to 27.5 °C. Calculate the enthalpy change for the rxn, assuming that the calorimeter loses only a negligible quantity of heat, that the total volume of the solution is 100 mL, that its density is 1.0 g/mL, and that its specific heat is 4.18 J/ g-K.

Solution -q solution = -(specific heat of solution)x(grams of soln)xΔT=q rxn -[( 4.18 J/ g-K) x (50 g+50 g)x ( ) ] =q rxn J =q rxn kJ =q rxn M= n/V=> n= MV => 1.0 x = 0.05 mol HCl 1.0 x = 0.05 mol NaOH NaOH(aq) + HCl(aq)  NaCl(aq) + H2O(l) 1: 1 ratio between NaOH and HCl in the balanced equation

Solution kJ =q rxn NaOH(aq) + HCl(aq)  NaCl(aq) + H2O(l) 1: 1 ratio between NaOH and HCl in the balanced equation 0.05 mol HCl reacted w/ 0.05 mol NaOH ΔH rxn = q rxn / number of moles of the acid/base reacted ΔH rxn = kJ / 0.05 mol ΔH rxn = kJ/mol

2)BOMB CALORIMETER(CONSTANT- VOLUME) It’s usually used to determine “molar heat of combustion (ΔH° comb )” of substances. molar heat of combustion is the enthalpy change when 1 mole of the substance undergoes a complete combustion in excess oxygen under standard conditions. It’s always negative in sign.

Qrxn= - [Qwater + Qmetal] Qrxn = - [(m w.c w.ΔT) + (m metal. c metal. ΔT)] OR Qrxn = - [(m w.c w ) + (m metal. c metal )]. ΔT If the calorimeter cup is made of a different material (e.g. a metal): Q rxn = - C cal x ΔT

2)BOMB CALORIMETER(CONSTANT- VOLUME) We calculate the heat evolved by the rxn with: Q rxn = - C cal x ΔT

Example 2 data above is from an experiment used to measure the enthalpy change for the combustion of 1 mole of glucose (C 6 H 12 O 6(s) ). The time-temperature data was taken from a data-logging software programme.

Mass of sample of glucose, m = g Heat capacity of the system, Csystem = kJ K–1 ( C : 12 ; H: 1 ; O : 16 ) (a)Calculate ΔT, for the water, surrounding the chamber in the calorimeter. (b)Determine the amount, in moles, of glucose. (c)Calculate the enthalpy change for the combustion of 1 mole of glucose.

solution A) ΔT= =1.77°C B) n=m/M n= 1.389/ 180= mol=0.008mol C) Qrxn= -C ΔT= x1.77= kJ ΔH comb = kJ/ mol= kJ/mol ΔH comb = kJ/mol

Example 3 Methyl hydrazine (CH 6 N 2 ) is commonly used as a liquid rocket fuel. The combustion of methyl hydrazine w/ oxygen produces N 2 (g), CO 2 (g), and H 2 O(l). When 4.00 g of methyl hydrazine is combusted in a bomb calorimeter, the temperature of the calorimeter increases from °C to 39.50°C. In a separate experiment the heat capacity of the calorimeter is measured to be kJ/°C. What is heat of reaction for the combustion of a mole of methyl hydrazine in this calorimeter? (N: g/mol, H: 1.01g/mol, C: g/mol)

Solution - (heat capacity of the calorimeter)xΔT=q rxn - (7.794 kJ/°C) x (39.50 °C °C) kJ =q rxn Molar mass of CH 6 N 2 = (1x x x14.01)= g/mol n=mass/molar mass=> n=4.00g / gmol -1 n= mol mol CH 6 N 2 combusts kJ is released 1 mol CH 6 N 2 combusts ? ? = kJ/mol