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Thermodynamic Analysis of NH3 Decomposition

The document discusses the thermal decomposition of ammonia (NH3) into nitrogen (N2) and hydrogen (H2) at constant pressure, providing equations for the reaction heat capacity (ΔrxnCp), enthalpy (ΔrxnH), and equilibrium constant (Kp) as functions of temperature. It includes specific heat capacity formulas for NH3, N2, and H2, and outlines a MATLAB script used to estimate the equilibrium conversion of NH3 over a temperature range of 0 to 1000 °C. The results indicate that NH3 conversion increases with temperature, achieving near-complete decomposition at higher temperatures.

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26 views9 pages

Thermodynamic Analysis of NH3 Decomposition

The document discusses the thermal decomposition of ammonia (NH3) into nitrogen (N2) and hydrogen (H2) at constant pressure, providing equations for the reaction heat capacity (ΔrxnCp), enthalpy (ΔrxnH), and equilibrium constant (Kp) as functions of temperature. It includes specific heat capacity formulas for NH3, N2, and H2, and outlines a MATLAB script used to estimate the equilibrium conversion of NH3 over a temperature range of 0 to 1000 °C. The results indicate that NH3 conversion increases with temperature, achieving near-complete decomposition at higher temperatures.

Uploaded by

tai.nguyen22042006
Copyright
© All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd

2. Decompose 1.

00 mol NH3 as follows: 2NH3 (g) = N2 (g) + 3H2 at constant total pressure P =
1.00 bar. Using the given tables in this subjects to take thermodynamic properties, then:

a/ Find the equation of ΔrxnCp as a function of temperature.

In this problem, we consider the thermal decomposition of ammonia in the gas phase and we
devide both side of the reaction for 2 to ensure that only 1 mol of NH 3 participates in the
decomposition reaction:

2𝑁𝐻3 (𝑔) = 𝑁2 (𝑔) + 3𝐻2 (𝑔)

If we want to express the formular for ∆𝑟𝑥𝑛 𝐶𝑃 (𝑇), we need the expression for each 𝐶𝑃 of the
elements as a function of temperature. The methology to solve this problem is described by P. J.
Linstrom and W. G. Mallard, Eds. (2005) by giving the formula:

𝑐𝑃
= 𝐴 + 𝐵𝑇 + 𝐶𝑇 2 + 𝐷𝑇 −2 + 𝐸𝑇 3 with 𝑇 in [K]
𝑅

and the following table:

Figure 1. Heat Capacity of Ideal Gas: Inorganic Compounds [1].


For NH3:

𝐶𝑝 = 𝑅 × (3.5778 + 3.02 × 10−3 × 𝑇 + (−0.186) × 10−5 × 𝑇 −2 (𝐽. 𝐾 −1 ),

with 𝑇 ∈ [298; 1800] (K)

For N2:

𝐶𝑝 = 𝑅 × (3.280 + 0.593 × 10−3 × 𝑇 + 0.04 × 10−5 × 𝑇 −2 (𝐽. 𝐾 −1 ),

with 𝑇 ∈ [298; 2000] (K)

For

𝐶𝑝 = 𝑅 × (3.249 + 0.422 × 10−3 × 𝑇 + 0.083 × 10−5 × 𝑇 −2 (𝐽. 𝐾 −1 ),

with 𝑇 ∈ [298; 3000] (K)

At that point, the conditions of the problem become:

[298; 1800] ∩ [298; 2000] ∩ [298; 3000] = [298; 1800] (K)

The reaction heat capacity is obtained from the molar heat capacities of each species involved,
using the general relation:

∆𝑟𝑥𝑛 𝐶𝑃 (𝑇) = ∑ 𝑣𝑖 𝐶𝑃,𝑖 (𝑇) − ∑ 𝑣𝑗 𝐶𝑃,𝑗 (𝑇)


𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠

where 𝑣 denotes the stoichiometric coefficients.

By applying the previous formula, we will obtain the equation for ∆𝑟𝑥𝑛 𝐶𝑃 (𝑇):

∆𝑟𝑥𝑛 𝐶𝑃 = 𝐶𝑃 (𝑁2 , 𝑔) + 3𝐶𝑃 (𝐻2 , 𝑔) − 2𝐶𝑃 (𝑁𝐻3 , 𝑔)

From that we can obtain the equation for ∆𝑟𝑥𝑛 𝐶𝑃 as the function of temperature:
∆𝑟𝑥𝑛 𝐶𝑃 = 𝑅 × (5.87 − 4.18 × 10−3 × 𝑇 + 0.66 × 10−5 × 𝑇 −2 ) (𝐽. 𝐾 −1 )

b/ Find the equation of ΔrxnH as a function of temperature.

We have enthalpy of reaction at temperature T if we start at 298K:

𝑇
∆𝑟 𝐻(𝑇) = ∆𝑟 𝐻(298) + ∫ ∆𝑟𝑥𝑛 𝐶𝑝 𝑑𝑇
298

𝑇
= ∆𝑟 𝐻(298) + ∫ ∆𝑟𝑥𝑛 𝐶𝑝 𝑑𝑇
298

𝑇
= ∆𝑟 𝐻(298) + ∫ 𝑅 × (5.87 − 4.18 × 10−3 × 𝑇 + 0.66 × 10−5 × 𝑇 −2 )𝑑𝑇
298

𝑇2 1
= ∆𝑟 𝐻(298) + 𝑅 (5.87𝑇 − 4.18 × 10−3 × − 0.66 × 10−5 × ) − 13000.26
2 𝑇

We consider ∆𝑟 𝐻(298) similar to the standard enthalpy of reaction ∆𝑟 𝐻°(298)

So the enthalpy of reaction is:

∆𝑟 𝐻° = 3∆𝑓 𝐻°(𝐻2 ) + ∆𝑓 𝐻°(𝑁2 ) − 2∆𝑓 𝐻°(𝑁𝐻3 ) = 92.22 × 103 (𝐽)

In conclusion, the equation of ΔrxnH as a function of temperature is:

3 −3
𝑇2 1
∆𝑟 𝐻(𝑇) = 92.22 × 10 + 𝑅 (5.87𝑇 − 4.18 × 10 × − 0.66 × 10−5 × ) − 13000.26
2 𝑇

𝑇2 1
= 79219.74 + 𝑅 (5.87𝑇 − 4.18 × 10−3 × − 0.66 × 10−5 × ) (𝐽)
2 𝑇

c/ Find the equation of Kp as a function of temperature.


We have the equation for Kp is:

𝑑𝑙𝑛𝐾𝑃 ∆𝐻(𝑇)
=
𝑑𝑇 𝑅𝑇 2

𝑇
∆𝐻(𝑇)
→ 𝑙𝑛𝐾𝑃 (𝑇) = 𝑙𝑛𝐾𝑃 (298) + ∫ 2
𝑑𝑇
298 𝑅𝑇

𝑇2 1
𝑇 79219.74 + 𝑅 (5.87𝑇 − 4.18 × 10−3 × 2 − 0.66 × 10−5 × 𝑇)
= 𝑙𝑛𝐾𝑃 (298) + ∫ 𝑑𝑇
298 𝑅𝑇 2

79219.74 −3
0.66 × 10−5
= 𝑙𝑛𝐾𝑃 (298) − + 5.87𝑙𝑛𝑇 − 2.09 × 10 × 𝑇 + + 0.84
𝑅𝑇 𝑇2 × 2

Now we need to calculate 𝑙𝑛𝐾𝑃 (298):

∆𝐺°(298) ∆𝐺°𝑓 (𝑁2 ) + 3∆𝐺°𝑓 (𝑁𝐻2 ) − ∆𝐺°𝑓 (𝑁𝐻3 )


𝑙𝑛𝐾𝑃 (298) = − =−
𝑅𝑇 𝑅𝑇

0 + 3 × 0 − (−16.45 × 103 )
𝑙𝑛𝐾𝑃 (298) = − = −6.640
𝑅𝑇

79219.74 0.66 × 10−5


→ 𝑙𝑛𝐾𝑃 (𝑇) = −6.640 − + 5.87𝑙𝑛𝑇 − 2.09 × 10−3 × 𝑇 + + 0.844
𝑅𝑇 𝑇2 × 2

79219.74 0.66 × 10−5


→ 𝑙𝑛𝐾𝑃 (𝑇) = −5.796 − + 5.87𝑙𝑛𝑇 − 2.09 × 10−3 × 𝑇 +
𝑅𝑇 𝑇2 × 2

We also have:

𝐾𝑃,𝑇 = 𝑒 𝑙𝑛𝐾𝑃,𝑇

Therefore:

79219.74 0.66×10−5
−5.796− +5.87𝑙𝑛𝑇−2.09×10−3 ×𝑇+
𝐾𝑃,𝑇 = 𝑒 𝑅𝑇 𝑇 2 ×2
d/ Estimate the conversion of NH3 in a range of 0–1000 °C (increase each 50 °C: 0, 50, 100,...,
1000 °C). Draw a diagram to show the conversion of NH3 as a function of temperature.

We need to convert variable T of the equation into t (°C) instead of T (K):

79219.74 0.66×10−5
−5.796− +5.87 ln(𝑡+273)−2.09×10−3 ×(𝑡+273)+
𝐾𝑃,𝑡 = 𝑒 𝑅(𝑡+273) (𝑡+273)2 ×2

In the next step, we need the expression for 𝐾𝑥 and calculate ∆𝑛:

2𝑁𝐻3 (𝑔) = 𝑁2 (𝑔) + 3𝐻2 (𝑔)

Initial: 1 0 0

1 3
React: x 𝑥 𝑥
2 2

1 3
Equilibrum: 1−𝑥 𝑥 𝑥
2 2

So we can calculate the total mole at equilibrium:

𝑛𝑡𝑜𝑡 = 1 + 𝑥 (𝑚𝑜𝑙)

Mole fractions:

1 3
1−𝑥 𝑥 𝑥
𝑦𝑁𝐻3 = , 𝑦𝑁2 = 2 , 𝑦𝐻2 = 2
1+𝑥 1+𝑥 1+𝑥

1 3 3
3
2 𝑥 (2 𝑥)
𝑦𝑁2 × (𝑦𝐻2 ) (1 + 𝑥)4 27 𝑥4
𝐾𝑥 = = = ×
(𝑦𝑁𝐻3 )2 (1 − 𝑥)2 16 (1 + 𝑥)2 × (1 − 𝑥)2
(1 + 𝑥)2

We use the formula of effect of total pressure to obtain the equation of equilibrium constant
expressed in terms of mole fractions:
𝐾𝑝 = 𝐾𝑥 . 𝑃 ∆𝑛

79219.74 0.66×10−5
−5.796− +5.87 ln(𝑡+273)−2.09×10−3 ×(𝑡+273)+
(𝑡+273)2 ×2
27 𝑥4
→ 𝑒 𝑅(𝑡+273) = × 2 2
× 22
16 (1 (1
+ 𝑥) × − 𝑥)
The following MATLAB script was used to estimate the equilibrium conversion of ammonia (NH₃)
over a temperature range from 0 to 1000 °C. The script computes the degree of decomposition as
a function of temperature using the given thermodynamic parameters.
clc; clear;

R = 8.314; % Gas constant J/mol·K


t_C = [0 25 50:50:1000]; % Temperature in °C, including 25°C
T = t_C + 273; % Temperature in Kelvin
x_values = zeros(size(T));
for i = 1:length(T)
if t_C(i) < 25
x_values(i) = NaN; % Ignore value below 25°C
else
% Compute equilibrium constant Kp for current temperature
Kp = exp(-5.796 - 79219.74/(R*T(i)) + 5.87*log(T(i)) - 2.09e-3*T(i) +
0.66e-5/(2*T(i)^2));

% Create a grid of x values from 0 to 1


x_grid = linspace(0,1,10000);
% Compute f(x) to find root closest to zero
f_val = 6.75*x_grid.^4 ./ ((1+x_grid).^2 .* (1-x_grid).^2) - Kp;

% Find the x value where f_val is closest to 0


[~, idx] = min(abs(f_val));
x_values(i) = x_grid(idx);
end
end
figure;
plot(t_C, x_values, '-o','LineWidth',1.5); % Plot NH3 conversion vs temperature
xlabel('Temperature (°C)'); % X-axis label
ylabel('Degree of NH_3 decomposition x'); % Y-axis label
grid on;
ylim([0 1]);
% Add specific x-axis ticks
xticks([0 25 50 100 150 200 250 300 350 400 450 500 550 600 650 700 750 800 850
900 950 1000]);
Listing 1. MATLAB script used to calculate the equilibrium conversion of NH₃ over a
temperature range from 0 to 1000 °C.

The conversion of NH₃ at equilibrium over the temperature range is illustrated in Figure 2. It can
be seen that the conversion increases with temperature, reaching near-complete decomposition at
high temperatures.

Figure 2. Variation of NH3 conversion with temperature (25-1000 °C)

Figure 1 shows the estimated conversion of NH₃ as a function of temperature. Temperatures below
25 °C were not considered because the original heat capacity data (𝐶𝑃 ) used for the calculations
are only valid in the temperature range 298 K to 1800 K, making equilibrium calculations below
this range unreliable.
References

[1] P. J. Linstrom and W. G. Mallard, Eds., NIST Chemistry WebBook, NIST Standard Reference
Database Number 69, National Institute of Standards and Technology, Gaithersburg, MD, USA,
June 2005. [Online]. Available: [Link]

Common questions

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Using the gas constant (R) consistently is crucial for harmonizing units across thermodynamic computations, ensuring accuracy and coherence in calculated values for heat capacity, enthalpy, and equilibrium constants. It maintains consistency between volumetric, pressure, and energy parameters, essential for the precise interpretation of energetic and equilibrium characteristics in reactions such as ammonia decomposition .

Converting the temperature from Kelvin to degrees Celsius in the analysis allows for the expression of results in a more conventional and readily interpretable format, particularly when plotting conversion trends versus temperature. Celsius is a more intuitive scale for practical applications, aiding in visualizing and assessing decomposition behavior in typical laboratory or industrial settings .

The conversion of NH3 increases with temperature due to the endothermic nature of the decomposition reaction, reaching near-complete decomposition at high temperatures. A MATLAB script estimates this conversion over a range from 0 to 1000 °C by calculating the equilibrium constant Kp for each temperature and solving the equilibrium equation 27/16 x x^4/((1+x)^2(1-x)^2) against the calculated Kp. Conversion is found by minimizing the discrepancy between Kp and the reaction quotient .

Stoichiometric coefficients are critical in determining the heat capacity of reaction products as they indicate the proportion of each product involved. In ammonia decomposition, coefficients define the amount of N2 and H2 formed, affecting the overall reaction heat capacity calculation. The equation ΔrxnCp(T) = ΣviCp,i(T) for products - ΣvjCp,j(T) for reactants incorporates these coefficients, making it essential to accurately account for the stoichiometry ([1 N2, 3 H2] per 2 NH3) to obtain correct heat capacity changes .

The change in enthalpy of reaction (ΔrxnH) as a function of temperature is given by ΔrxnH(T) = ΔrxnH(298) + R(5.87T - 4.18 x 10^(-3)T^2/2 - 0.66 x 10^(-5)/T) - 13000.26. This expression reflects the temperature dependence of reaction enthalpy, integrating the heat capacity change (ΔrxnCp). It highlights the endothermic nature of ammonia decomposition, which requires heat absorption to proceed .

It is inaccurate to calculate the equilibrium conversion of NH3 below 25 °C because the provided thermodynamic data, such as heat capacities (Cp), are only valid in the temperature range from 298 K to 1800 K. Outside this range, the calculations are unreliable as the data does not represent the physical behavior of the gases, leading to potentially incorrect equilibrium predictions .

The change in reaction heat capacity (∆rxnCp) for the decomposition of ammonia is derived by calculating the difference in heat capacities of the products and reactants. For the reaction 2NH3 = N2 + 3H2, the heat capacity of each component is expressed as Cp/R = A + BT + CT^2 + DT^(-2) + ET^3, with specific constants provided for each gas. The total reaction heat capacity is given by ΔrxnCp(T) = Cp(N2, g) + 3Cp(H2, g) - 2Cp(NH3, g). This results in ΔrxnCp being proportional to R times the coefficients (5.87 - 4.18 x 10^(-3) x T + 0.66 x 10^(-5) x T^(-2)).

The term lnKp(298) in the equilibrium constant expression accounts for the standard free energy change at 298 K. It provides a reference point for calculating Kp at other temperatures, incorporating the Gibbs free energy contributions of reactants and products under standard conditions. This term is crucial for anchoring the temperature-dependent part of the equation, ensuring all temperature calculations are relative to this baseline free energy difference .

The equilibrium constant (Kp) for ammonia decomposition as a function of temperature is calculated using the relation dlnKp/dT = ΔH(T)/(RT^2). Solving this differential equation by integrating yields lnKp(T) = lnKp(298) + ∫(ΔH(T)/RT^2)dT from 298 to T. This integral, when evaluated using the specific heat capacities and reaction enthalpy, results in lnKp(T) = -5.796 - 79219.74/(RT) + 5.87lnT - 2.09x10^(-3)T + 0.66x10^(-5)T^2 .

The MATLAB script begins by initializing constants and defining the temperature range from 0 to 1000 °C. It calculates the equilibrium constant Kp at each temperature by integrating the heat capacity data. The script also constructs a grid of conversion values (x) and computes a function f(x) to identify the conversion level where the discrepancy with Kp is minimized. Key outputs include the degree of NH3 decomposition as a function of temperature, which is plotted to show conversion increasing with temperature .

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