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5.60 Thermodynamics & Kinetics

Spring 2008

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5.60 Spring 2008

Lecture #7

page 1

Calorimetry
The objective is to measure
Hrx (T1 )
isothermal constant p

Reactants (T1) Constant pressure

CALORIMETER

Products (T1)

(for solutions)

reaction thermometer

Adiabatic Constant p

I) II)

HI HII
Hrx (T1 )

React. (T1) + Cal. (T1) Prod. (T2) + Cal. (T2) React. (T1) + Cal. (T1)

adiabatic constant p

Prod. (T2) + Cal. (T2) Prod. (T1) + Cal. (T1) Prod. (T1) + Cal. (T1)

constant p

______________________________________________________

Hrx (T1 ) = HI + HII

constant p

(I) Purpose is to measure (T2 - T1)

Adiabatic, const. p

qp = 0

HI = 0

(II) Purpose is to measure heat qp needed to take prod. + cal. from T2 back to T1.
qp = C p ( Prod . + Cal . ) dT = HII
T1 T2

Hrx (T1 ) = T C p ( Prod . + Cal . )dT T C pcal dT = C pcal T

1 1

T2

T2

5.60 Spring 2008

Lecture #7

page 2

Constant volume

(when gases involved)

CALORIMETER

reaction thermometer

Adiabatic Constant V

I) II)

U I

React. (T1) + Cal. (T1) Prod. (T2) + Cal. (T2) React. (T1) + Cal. (T1)

adiabatic constant V

Prod. (T2) + Cal. (T2) Prod. (T1) + Cal. (T1) Prod. (T1) + Cal. (T1)

UII
Urx (T1 )

______________________________________________________

constant V

constant V

Urx (T1 ) = UI + UII

(I) Purpose is to measure (T2 - T1)

Adiabatic, const. V

qV = 0

UI = 0

(II) Purpose is to measure heat qV needed to take prod. + cal. from T2 back to T1.
qV = CV ( Prod . + Cal . ) dT = UII
T1 T2

Urx (T1 ) = T CV ( Prod . + Cal . )dT T CVcal dT = CVcal T

1 1

T2

T2

Now use

H = U + pV

or

H = U + ( pV

is from gases.

Assume only significant contribution to ( pV

5.60 Spring 2008

Lecture #7

page 3

Ideal gas Isothermal

( pV ) = R (nT

T =T1

( pV ) = RT1
ngas

Hrx (T1 ) = Urx (T1 ) + RT1 ngas Hrx (T1 ) = CV ( Prod . + Cal . ) dT + RT1 ngas CVcal T + RT1 ngas
T1 T2

Difference between U and H small but measurable e.g. 4 HCl(g) + O2(g) = 2 H2O(l) + 2 Cl2(g)

T1 = 298.15 K
Urx (T1 ) = -195.0 kJ

ngas = -3 moles

Hrx (T1 ) = -195.0 kJ + (-3 mol)( 298.15 K)(8.314x10-3 kJ/K-mol)

= -202.43 kJ Now lets imagine really running this reaction in a constant-V calorimeter with Cv = 10 kJ/K Calorimeter thermal mass >> product thermal mass Heat goes to changing calorimeter T Often no need to know product Cp or CV value

5.60 Spring 2008

Lecture #7

page 4

Really bond enthalpies, but usually (pV) << difference 1) 2) e.g.

Bond energies: An approximate method for estimating Hf

Measure bond energies for known compounds Use them to estimate Hf for unknown compounds CH4(g) = C(graphite) + 2 H2(g) C(graphite) = C(g) 2 H2(g) = 4 H(g)
CH4(g) = C(g) + 4 H(g)
H
H- C -H
| |

HI = Hf,CH

2HH ( atomization )
2

HC ( atomization )

____________________________________________________________

H = 4BC-H

BC-H = 416.2 kJ

4 BC-H = Hf,CH + HC (atom .) + 2HH

4

2 ( atom .)

BC H = 416.2 kJ

H H
| | | |

C2H6(g) = C(g) + 6 H(g)

H- C - C -H H H

H = BC-C + 6BC-H = Hf,C H + 2HC (atom .) + 3HH (atom .) BC C = 342 kJ

2 6 2

Now estimate Hf for n-pentane, C5H12 5 C(graphite) = 5 C(g) 6 H2(g) = 12 H(g) 5 C(g) + 12 H(g) = C5H12(g)

CH3-CH2- CH2- CH2-CH3

5HC (atom .)

____________________________________________________________

H (4Bc c + 12B C H Hf,C H

5 12

6HH

2 ( atom .)

5 C(graphite) + 6 H2(g) = C5H12(g)

5.60 Spring 2008

Lecture #7

page 5

Hfo,C 5H12 (4Bc c + 12B C H ) + 5HC (atom .) + 6HH2( atom .) ~ -152.6 kJ (estimated)
Actual Hf,C H (n-pentane ) = -146.4 kJ

5 12

CH3

But

CH3 - C -CH3
|

is also C5H12 with 4 C-C bonds, 12 C-H bonds

CH3

Hf,C H ~ -152.6 kJ (estimated using bond energies)

5 12

Actual Hf,C H (neopentane ) = -166.1 kJ

5 12