17.04 The Standard State Gibbs Energy of Reaction

Standard State Gibbs Energy of Reaction (4:19)

Standard State Gibbs Energy of Reaction (4:19) (msu.edu)

The standard state Gibbs energy of reaction depends only on temperature. Thus the equilibrium constant is also dependent only on temperature. The fugacities of the components in the reacting mixture change until the argument in the logarithm term reaches the value given by the equilibrium constant.

Comprehension Questions:

1. Calculate the heat of reaction for CO + 2H2 = CH3OH at 298K.
2. Calculate the Gibbs energy of reaction for CO + 2H2 = CH3OH at 298K.
3. For the reaction of CO + 2H2 = CH3OH, does Ka (equilibrium constant) increase, decrease, or stay the same as we increase the pressure?

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17.05 - Effect of Pressure, Inerts, Feed Ratios

How to push, pull, persuade a reaction (3:32)

How to push, pull, persuade a reaction (3:32) (msu.edu)

Pressure can be used to influence conversion for reactions where gas phase species are present. Feed ratios, inerts, or simultaneous reactions can also be used.

Comprehension Questions:

1. The principle by which a change in temperature, pressure, or concentration leads to a counteracting change in equilibrium is known as:_____.
2. For the reaction: CO + 2H2 = CH3OH, an increase in pressure will cause the products to: ___ (decrease, increase, or be unaffected). Explain.
2. For the reaction: CH4 + H2O = CO + 3H2, an increase in pressure will cause the products to: ___ (decrease, increase, or be unaffected). Explain. (FYI: this reaction, known as "steam reforming" is an important step in making chemicals from natural gas.)
3. For the reaction: CO + 2H2 = CH3OH, adding an inert component will cause the products to: ___ (decrease, increase, or be unaffected). Explain.
4. We discuss temperature effects in detail later, but for now you should be able to make predictions based on ____ principle (cf. #1 above). An exothermic reaction gives off heat. Therefore, adding heat to an exothermic reaction (ie. raising the temperature) will cause the products to: ___ (decrease, increase, or be unaffected). Explain.
5. For the reaction: H2O + CO = H2 + CO2, an increase in pressure will cause the products to: ___ (decrease, increase, or be unaffected). Explain. (As a first approximation, you may neglect deviations from ideal gas behavior, but then discuss the effect these deviations would have if you did take them into account. Which component's fugacity would be most affected by these deviations and how do these deviations change with pressure?)
6. For the reaction: coal + H2O = CO + H2, an increase in pressure will cause the products to: ___ (decrease, increase, or be unaffected). Explain. (Hint: carbon in the form of coal is solid and does not exist in the vapor phase. cf. section 17.14. It might be helpful to think of the reverse reaction, known as coking, where the solid carbon precipitates from the gas. This is a very simple example of simultaneous reaction and phase equilibrium.)
7. For the reaction: CO + 2H2 = CH3OH, adding an inert liquid to the reactor through which all products are removed will cause the products to: ___ (decrease, increase, or be unaffected). Explain. (Hint: this is a bit more sophisticated example of simultaneous reaction and phase equilibrium. How will the inert liquid alter the concentrations in the vapor? Remember that the fugacities are proportional to the gaseous partial pressures.)

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KeysToCheRxrs

Partial pressures and reactor sizing are among the keys to chemical engineering calculations (uakron.edu, 7 min, review from Section 1.6). Partial pressures (uakron.edu, 7 min) also play an essential role in reaction equilibrium calculations. Partial pressure calculations basically involve straightforward mass balances, but specific vocabulary and a need for systematic precision can cause difficulty. The calculations involve six elements that must be carefully computed:

(1) Stoichiometry - the reaction equation must be stoichiometrically balanced such that the number of atoms of each element are the same on both sides of the equation. This balance is achieved by adjusting the stoichiometric coefficients. The change in the number of moles of each component must be in correct stoichiometric proportions relative to the "key component." Inert compounds (see below) are NOT included in the stoichiometric equation. For the example in this presentation, the objective of the reactor is to oxidize carbon monoxide (CO) in a catalytic converter by reacting it with oxygen (O2). So, CO + 0.5 O2 = CO2.
(2) Limiting reactant (aka. "key component") - It is common to feed an excess of one of the components in order to promote complete conversion of the other components. The limiting reactant is the component that is NOT in excess. For this example, O2 is fed in excess so that CO conversion can be promoted. CO becomes the limiting reactant in that case and conversion must be computed relative to CO, NOT O2. If you think about it, expressing the conversion with respect to the excess component would mean that 100% conversion could result in a negative mole number for the limiting reactant. Such an implication is obviously physically impossible (and potentially embarrassing if you appear not to know that).
(3) %Excess - The number of moles of an excess component in the feed is (1+Xs) times the stoichiometric amount relative to the key component, where the stoichiometric amount is the number of moles necessary to perfectly balance the key component, and Xs is the fractional form of the %excess. For this example, the stoichiometric ratio of CO:O2 would be 1:0.5 and for 50% excess, Xs = 0.50, and the actual ratio would be 1:0.75.
(4) %Conversion - the %conversion is the fraction of the entering amount of the limiting reactant that is transformed into product(s). Note that this might be different from the "extent of reaction," ξ. For example, if 50 moles/h of CO enter the reactor and the conversion is 90%, then 5 moles of CO exit the reactor. If you express the number of moles of CO as 50-ξ, you might conclude that the moles of CO exiting the reactor is 49.1. Take a minute to think about what the words mean before you start to calculate, then make a mental estimate of what the results should be, then get out your calculator. Another common mistake is to apply the % conversion to all the components, wrongly including the excess component. For example, if 45 moles of CO react, then 22.5 moles of O2 react. With 50% excess O2 in the feed, the O2 exiting should be 37.5-22.5=15, NOT 3.75. This is what it means to be careful and systematic. You must compute the conversion of limiting reactant first, then compute the conversion of other components relative to the limiting reactant.
(5) Inerts - These are components that may enter the reactor by coincidence or convenience but do not participate in the reaction. Therefore, their number of moles exiting the reactor is simply equal to their number of moles entering the reactor. A common mistake is to apply the %conversion to all components entering the reactor, including the inerts. In this example, the source of O2 is air, with roughly 4:1 ratio of nitrogen (N2) to O2. The N2 is inert.
(6) Total Pressure - Once the mole numbers and mole fractions have been computed, don't forget to multiply the mole fractions by the total pressure to get the partial pressure. The partial pressure is equal to the mole fraction only in the case that the reactor operates at 1.00 bar.

Comprehension Questions:

1. What is the value of the total pressure (bar) applied in the presentation of this example?
2. What equation is used to compute the mole number of O2? What is the final overall equation used to compute P_O2?
3. Suppose 100 moles/h of ammonia (NH3) at 100bars is to be produced from N2 and hydrogen (H2) with 10% excess N2. Methane (CH4) is included with the N2+H2 as a result of the synthesis process with a ratio of 1:10 CH4:H2. (a) Write a stoichiometrically balanced equation (b) Identify the limiting reactant (c) Calculate the number of moles and partial pressures of each component entering the reactor. (d) Calculate the number of moles and partial pressures of each component exiting the reactor assuming 25% conversion.

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17.06 Determining the Spontaneity of Reactions

Which way will a reaction go? (3:40)

Which way will a reaction go? (3:40) (msu.edu)

When both reactants and products are present in a reactng mixture, the direction the reaction will proceed is not necessarily indicated by the sign of ΔG^o or Ka. Rather, it is determined by ΔG. This screencasts provides guidance for understanding this concept.

Comprehension Questions: (Hint: review Example 17.1 before answering.)

1. CO and H2 are fed in a 2:1 ratio to a reactor at 500K and 20 bars with a catalyst that favors only CH3OH as its product. When the conversion of H2 is 32%, will the reaction go forwards towards product or back to reactants?
2. CO and H2 are fed in a 2:1 ratio to a reactor at 500K and 20 bars with a catalyst that favors only CH3OH as its product. When the conversion of CO is 52%, will the reaction go forwards towards product or back to reactants?
3. CO and H2 are fed in a 1:1 ratio to a reactor at 500K and 20 bars with a catalyst that favors only CH3OH as its product. When the conversion of H2 is 42%, will the reaction go forwards towards product or back to reactants?
4. CO and H2 are fed in a 1:1 ratio to a reactor at 500K and 20 bars with a catalyst that favors only CH3OH as its product. When the conversion of H2 is 42%, will the reaction go forwards towards product or back to reactants?

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17.07 - Temperature Dependence of Ka

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Example 17.4 and 17.5 solved using Kcalc.xlsx (6:01)

Example 17.4 and 17.5 solved using Kcalc.xlsx (6:01) (msu.edu)

The full form of the temperature dependence of Ka is implemented in Kcalc.xlsx and Kcalc.m. This screecast covers the use of Kcalc.xlsx for Example 17.4 and Example 17.5 of the textbook.

Comprehension Questions:

1. CO and H2 are fed in a 2:1 ratio to a reactor at 500K and 20 bars with a catalyst that favors only CH3OH as its product. Calculate ΔG_Rº and ΔH_Rº.
2. CO and H2 are fed in a 1:1 ratio to a reactor at 500K and 20 bars with a catalyst that favors only CH3OH as its product. Calculate ΔG_Rº and ΔH_Rº.
3. CO and H2 are fed in a 1:1 ratio to a reactor at 600K and 20 bars with a catalyst that favors only CH3OH as its product. Calculate ΔG_Rº and ΔH_Rº.
4. CO and H2 are fed in a 1:1 ratio to a reactor at 500K and 20 bars with a catalyst that favors only CH3OH as its product. Calculate ΔG_Tº and ΔH_Tº. Check your answer for ΔG_Tº using the value given for K_ain Example 17.1.
5. CO and H2 are fed in a 1:1 ratio to a reactor at 600K and 10 bars with a catalyst that favors only CH3OH as its product. Calculate K_a, ΔG_Tº and ΔH_Tº.
6. CH3OH is fed to a reactor at 200ºC and 1 bar with a catalyst that produces CO and H2. Calculate K_a, ΔG_Tº and ΔH_Tº for this reaction and compare to the literature values given in Example 17.6 of Section 17.10.
7. CH3OH is fed to a reactor at 300ºC and 1 bar with a catalyst that produces CO and H2. Calculate K_a for this reaction and compare to the value given in Example 17.6 of Section 17.10. Give two reasons why the two estimates are not identical.

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Kcalc Bells&Whistles

You can customize Kcalc.xlsx (uakron.edu, 17min) to facilitate whatever calculations you may need to perform. This presentation shows how to implement VLOOKUP to automatically load the relevant Hf, Gf, and Cp values. It also shows how to automatically use the Cp/R value when a,b,c,d values for Cp are not available. Finally, it shows how a fairly general table of inlet flows, temperatures, and pressures can be used to set up the equilibrium conversion calculation. The initial set up is demonstrated for the dimethyl ether process, then revised to initiate solution of Example 17.9 for ammonia synthesis.

Comprehension Questions:

1. The video shows how the shortcut Van't Hof equation can be written as lnKa=A+B/T. What are the values of A and B for the dimethyl ether process when a reference temperature of 633K is used?
2. The video shows how the shortcut Van't Hof equation can be written as lnKa=A+B/T. What are the values of A and B for the ammonia synthesis process when a reference temperature of 600K is used?

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17.10 - Solving Equilibria for Multiple Reactions

Multiple Reaction Equilibria using Excel (8:48)

Multiple Reaction Equilibria using Excel (8:48) (msu.edu)

Example 17.6 (Section 17.10) solves two reactions for equilibrium simultaneously with Excel. To skip the problem set up and see how to use Excel variables jump to 5:15. To jump to the use of solver for two equations, jump to 7:15.

Comprehension Questions:

1. CH3OH is fed to a reactor at 200ºC and 3 bar with a catalyst that produces CO, H2, dimethyl ether, and H2O. Calculate the equilibrium extents of reaction and compositions of all species.
2. Diisopropylbenzene (DIPB) is a possible byproduct of the reaction of benzene with propylene to make cumene. If the reaction is conducted at 300C and 11 bars with a stoichiometric feed relative to the cumene reaction, calculate the equilibrium extents of reaction and compositions of all species.

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17.12 Energy Balances for Reactions

Adiabatic Ammonia Reactor

Equilibrium constants and adiabatic reactor calculations with Excel (uakron.edu, 6 min) We previously discussed adiabatic reactor calculations in Section 3.6 with application to the dimethyl ether process. At that time, we accepted the expression for equilibrium constant as given. In Chapter 17, we must recognize how to compute the equilibrium constant for ourselves. This presentation illustrates the calculations for Example 17.9. These kinds of calculations often occur in the context of an overall process, rather than in isolation. Therefore, the presentation shows how to apply Eqn 3.5b with pathway 2.6c to characterize the enthalpies of process streams and solve for the extent of reaction and adiabatic outlet temperature simultaneously.

Comprehension Questions:

1. Suppose the reactor inlet feed was: kmol/hr of 110 N2, 300 H2, 15NH3 and 16 CH4. Solve for the adiabatic reactor temperature and extent of reaction in that case.
2. Suppose the actual conversion was only 80% of the equilibrium conversion and the inlet feed was the same as given in part 1. Solve for the adiabatic reactor temperature and extent of reaction in that case.
3. Compute the stream attributes for this entire process assuming 85% of the equilibrium conversion and a feed (kmol/h) of 105 N2, 300 H2, 20 CH4 at 10bars and 200C. The distillation column operates at 10 bars with a partial condenser and splits of 99.99% on N2 and 2% on NH3. The recycle ratio is 19:1. Assume the compressors are 100% efficient and the reactor operates adiabatically with an inlet temperature of 400K and a pressure of 100bars. Report the molar flow rates of all outlet stream components.

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Chapter 17 - Reaction Equilibria

Chapter 17 - Reaction Equilibria

17.04 The Standard State Gibbs Energy of Reaction