Calorimetry

Measurement of heats of reactions Determination of E and H Calorimeter: a device for which the heat capacity, C, is known T qrxn

Calorimeters
There are two common types of calorimeter: constant pressure (coffee cup) constant volume (bomb) The heat capacity, Ccalorimeter, must be known or determined since qreaction = - Ccalorimeter T If qreaction is measured at constant V it is E If qreaction is measured at constant P it is H

Coffee Cup Example

1.0 L of 1.0 M Ba(NO3)2 at 25C was mixed with 1.0 L of 1.0 M Na2SO4 at 25C in a constant pressure calorimeter to form BaSO4(s). The final solution temperature was 28.1C . What is H and E per mole of BaSO4 formed?

qp = - (4.18 J g-1 K-1)(2000 g) (28.1C-25.0C) = -25,900 J H = -25.9 kJ Since (PV) ngasRT 0 E H= -25.9 kJ

Example: Constant P
2.0 mol of SO2(g) was reacted with 1.0 mol of O2(g) to form 2.0 mol of SO3(g) at 1.0 atm and 25C. If 198 kJ of energy was released as heat, what are H and E for this reaction? qrxn = qp = H = -198 kJ (PV) 0 so E = H - PV= H (ngas)RT = (-198,000 J) - (-1 mol)(8.314 J mol-1 K-1)(298 K) = -195.5 kJ

Bomb Calorimetry

Closed system (const V) so heat measured is qv Can measure very energetic reactions such as combustion

Enthalpy of Combustion, Hc
Hc is the enthalpy change when one mole of a compound is completely reacted with oxygen 1 C8H18 + 12 O2 8 CO2 + 9 H2O + heat

For hydrocarbons, the only products are CO2 and H2O bomb calorimetry is often the method of choice for this measurement

A bomb calorimeter was used to measure the heat of combustion of CH4(g). When 1.6 g of CH4(g) was burned in excess oxygen and the temperature increased by 7.8C. The heat capacity of the calorimeter is 11.3 kJ/C. What are E and H of combustion for CH4 at 25C? qv = -(11.8 kJ/C)(7.3C) = -88 kJ n = (1.6 g)/(16g/mol)= 0.10 mol Ec = -880 kJ/mol Hc = E + (ngas)RT = -880,000 J + (-2 mol)(8.314 J mol-1 K-1)(298 K) Hc = -885 kJ/mol

Example: Hc

Enthalpy Change of a Reaction

reactants
initial state

products
final state

Hreaction

H is a state function so Hreaction is a state function (independent of pathway) Hreaction = Hproducts - Hreactants

Hess's Law
state A H1 state C H2 H4 state B H3 state D

H4 = H1 + H2 + H3 H1 = ?

Using Hess's Law

Adding equations: H2(g) + Cl2(g) 2 HCl(g) H2O(l) H2(g) + O2(g) H2O(l) + Cl2(g) H = -185 kJ H = 286 kJ

2 HCl(g)+ O2(g) H = 101 kJ

Reversing equations: H2(g) + O2(g) H2O(l) Multiplying equations: 2 H2O(l) 2 H2(g) + O2(g)

H = -286 kJ

H = 572 kJ

Enthalpy of Formation Hf

The enthalpy of forming 1 mole of a substance from its constituent elements. Useful for determining the enthalpy of ANY reaction

Enthalpy of Formation

Standard States
Definitions of Standard States : Gases: gas at partial pressure of 1 atm Solutes: a conc. of 1M at an applied P of 1atm Liquids or solids: the pure liquid or solid at 1atm Elements: the elemental form that exists at 1 atm Note: A degree symbol () indicates a process where all reactants and products are at standard states

Standard Enthalpy of Formation (Hf- delta H naught f)

Definition: The enthalpy change for the formation of 1 mole of a compound from its elements under standard state conditions Hf for an element in its standard state by this definition is exactly zero There is no standard temperature. Hf depends on temperature and is often tabulated at 298 K (25C)

reactants products Hreaction Hreaction = Hfproducts Hfreactants

Hf - example
e.g. Determine Hreaction at 298 K for : 4 NH3(g) + 7 O2(g) 4 NO2(g) + 6 H2O(l)

Look up in table of Hf values at 298 K: NH3(g) = - 46 kJ/mol O2(g) = 0 kJ/mol NO2(g) = +34 kJ/mol H2O(l) = - 286 kJ/mol Hreaction = 4 (34) + 6 (-286) 4 (-46) 7 (0) = - 1396 kJ

Enthalpy of Various Processes

Hf of Cdiamond
How would you determine this experimentally? C(graphite) + O2 (g) C(diamond)+ O2 (g) C(graphite) C(diamond) CO2(g) Hc,grap = -393.5 kJ CO2(g) Hc,diam = -395.4 kJ Hf = Hc,grap - Hc,diam = 1.9 kJ

How much energy would it take to convert 1.0 kg of ice at 0C to steam at 100C?

What minimum water flow would you need to cool a reactor that was producing 1000 kg/hr of ethanol from ethylene by hydrolysis at 25 C? C2H4 (g) + H2O(l) C2H5OH(l)

Assume water is 10C on intake and may not be released above 30C to meet environmental regulations.