Procedimento para aplicar correção ao cálculo da Entalpia em decorrência da alteração de temperatura.

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Procedimento para aplicar correção ao cálculo da Entalpia em decorrência da alteração de temperatura.

© All Rights Reserved

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The enthalpy changes for chemical reaction can be deduced for a range of

temperature.

For a chemical equation:

Reactants ---- Products

The enthalpy change for the reaction can be written as:

H = Hprod - Hreact

Where the product and reactants enthalpies imply the sum of the molar

enthalpies of the products and reactants in given chemical equation.

The derivative with respect to temperature is given as:

We can write this using heat-capacity terms:

Where (Cp)prod and (Cp)react imply the sum of the heat capacities of the

product and reactant species.

T2

[(H) / T]P

= H T - H T

2

T1

T2

Cp dT

T1

Since,

Cp = a + bT + (C/T2)

Thus, we have

H T - H T =

2

T2

Cp dT

T1

Using this equation we can calculate the enthalpy change at one temperature

from the enthalpy change at another temperature.

A more general expression for temperature dependence of the reaction

enthalpy change is obtained by developing an indefinite integral.

Thus, we get

H T =

Cp dT + const.

And

The constant term is evaluated by using the enthalpy change for the reaction

at 250C.

After calculating the constant term, the equation can be used to calculate the

enthalpy change at any other temperature.

Problem 1:

Calculate the enthalpy change for the industrially important shift-conversion

reaction CO (g) + H2O (g) -- CO2 (g) + H2 (g) at 1500 K.

Standard enthalpies of formation of CO (g), H2O (g), CO2 (g), H2 (g) are

-110.52, -241.82, -393.51 and 0 kJmol-1 respectively.

CO (g) + H2O (g) -- CO2 (g) + H2 (g)

H0 f =

-110.52

-241.82

-393.51

H0298

= -41.17 kJmol-1

a terms

b terms

c terms

28.41

30.54

44.22

27.28

0.00410 0.01029

0.00879

0.00326

-46,000

0

-862,000

50,000

a = 12.55

b = -2.34 10-3

b = -7.66 105

We have

----------- (1)

= 12.55 T +(1/2)(-2.34 10-3)(T2) -(-7.66 105) (1/T) +

const

---------- (2)

With H0 298.15 = -41,170 Jmol-1 and T = 298.15 K

We get the

Substituting the value for constant in equation (2)

(1/T) -47,380 J mol-1

For T = 1500 K

The Molar Heat Capacity Cp of monoatomic gases:

Using the classical kinetic-molecular theory and the quantum-mechanical

theory, the molar thermal internal energy due to translational motion is equal

to (3/2) RT

Cp = (H / T)p = (5/2)R = 20.78 J k-1 mol-1

Cp for Gases Composed of Diatomic Molecules:

Linear Molecules:

Linear Diatomic molecules have 3 translational degrees of freedom, 2

rotational degrees of freedom, and 1 vibrational degree of freedom.

The translational motion gives thermal energy of (1/2)RT per degree of

freedom.

(U - U0)trans = (3/2) RT

The heat-capacity contribution for translational motion is

The rotational motion gives thermal energy of (1/2)RT per degree of

freedom.

(U - U0)rot = (2/2)RT = RT

The heat-capacity contribution for rotational motion is

Crot = (U - U0)rot /T = R

The vibrational motion gives thermal energy of RT [ x / (ex-1)] per degree

of freedom where x = (vib / kT ).

(U - U0)vib = RT [ x / (ex-1)]

where x = (vib / kT )

The total heat capacity contribution for linear diatomic molecules (1 mole of

ideal gas) is given as:

= (3/2) R + R + R x2 ex / (ex -1)2

= (5/2) R + Cvib

And

Cp = Cv + R

= (5/2) R + Cvib + R

where x = (vib / kT )

= (7/2) R + Cvib

= 29.10 J K-1 mol-1 + Cvib

Non-linear molecules:

For non-linear molecules there are 3 rotational degrees of freedom, giving

rotational heat-capacity contribution as (3/2)R and (3n-6) vibrational degrees

of freedom, giving vibrational heat-capacity contribution as Cvib.

Thus

The total heat capacity contribution for non-linear diatomic molecules (1

mole of ideal gas) is given as:

= (3/2) R + (3/2)R + R x2 ex / (ex -1)2

= 3 R + Cvib

And

Cp = Cv + R

= 3 R + Cvib + R

= 4 R + Cvib

= 33.26 J K-1 mol-1 + Cvib

where x = (vib / kT )

Thermal Enthalpy:

Thermal enthalpy means the enthalpy that a sample has as a result of

quantum states with energies greater than the lowest-energy, or ground, state

being occupied.

At 0 K, only the lowest energy states are occupied and the thermal energy is

zero.

The thermal enthalpy at other temperatures can be expressed as

T

H0T - H00 =

C0p dT

0

250C or 298 K.

(H0T - H0298) = (H0T - H00) - (H0298 - H00)

= (H0T - H00) + (H00 - H0298)

and H - H0 to the enthalpy of Cl2 at 298 and at 1000K. Assume ideal-gas

behavior, and used the vibrational energy level spcing of 1.10 10-20 J per

molecule.

(U - U0)trans = (3/2) RT

(U - U0)rot = RT

(U - U0)vib = RT [ x / (ex-1)]

where x = (vib / kT )

At 298 K

x = (vib / kT ) = (1.10 10-20 J) / (1.381 10-23 JK-1 298 K)

= (1.10 103 ) / (1.381 298) = 2.67

[ x / (ex-1)] = 2.67 / (14.43 -1) = 0.198

At 1000 K

x = (vib / kT ) = (1.10 10-20 J) / (1.381 10-23 JK-1 1000 K)

= (1.10 103 ) / (1.381 1000) = 0.797

[ x / (ex-1)] = 0.797 / (2.218 -1) = 0.654

Now,

(U - U0) =(U - U0)trans + (U - U0)rot + (U - U0)vib

= (3/2) RT + RT + RT [ x / (ex-1)]

At 298 K

(U - U0)

= (3/2) RT + RT + RT 0.198

= 2.69 RT

= (2.69) ( 8.314 J K-1 mol-1) (298 K)

= 6684.48 J mol-1 = 6.68 kJ mol-1.

At 1000 K

(U - U0) = (3/2) RT + RT + RT 0.654

= 3.15 RT

= (3.15) ( 8.314 J K-1 mol-1) (1000K)

= 26189.10 J mol-1 = 26.18 kJ mol-1.

Now,

(H - H0) = (U - U0) + RT

AT 298 K

(H - H0) = (U - U0) + RT = 6684.48 J mol-1 + ( 8.314 J K-1 mol-1) (298 K)

= 6684.48 J mol-1 + 2477.57 J mol-1 = 9162.05 J mol-1 = 9.16 k J mol-1

AT 1000 K

(H - H0) = (U - U0) + RT = 26189.10 J mol-1 + ( 8.314 J K-1 mol-1) (1000 K)

= 26189.10 J mol-1 + 8314.00 J mol-1 = 34503.10 J mol-1= 34.5 k J mol-1

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