MCAT Physical : Thermochemistry and Energetics

Study concepts, example questions & explanations for MCAT Physical

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Example Questions

Example Question #5 : Gibbs Free Energy

A galvanic cell is set up, and is determined to have a standard cell potential of . Which prediction must be true, based on this voltage?

Possible Answers:

Electrons will flow toward the anode

Gibb's free energy is negative and the equilibrium constant is greater than one

The equilibrium constant is less than one

The reaction is not spontaneous

Correct answer:

Gibb's free energy is negative and the equilibrium constant is greater than one

Explanation:

There is an inherent relationship between cell potential, Gibb's free energy, and the equilibrium constant. Under standard conditions, a positive cell potential will signify a spontaneous reaction. This indicates that the Gibb's free energy () for the reaction must be negative. It also means that the equilibrium constant must be greater than one, indicating that the reaction favors the products over the reactants.

Electrons will always travel from the site of oxidation (anode) toward the site of reduction (cathode), regardless of reaction spontaneity.

Example Question #6 : Gibbs Free Energy

A scientist prepares an experiment to demonstrate the second law of thermodynamics for a chemistry class. In order to conduct the experiment, the scientist brings the class outside in January and gathers a cup of water and a portable stove.

The temperature outside is –10 degrees Celsius. The scientist asks the students to consider the following when answering his questions:

Gibbs Free Energy Formula:

ΔG = ΔH – TΔS 

 

Liquid-Solid Water Phase Change Reaction:

H2O(l) ⇌ H2O(s) + X

The scientist prepares two scenarios. 

Scenario 1:

The scientist buries the cup of water outside in the snow, returns to the classroom with his class for one hour, and the class then checks on the cup. They find that the water has frozen in the cup.

Scenario 2: 

The scientist then places the frozen cup of water on the stove and starts the gas. The class finds that the water melts quickly.

After the water melts, the scientist asks the students to consider two hypothetical scenarios as a thought experiment. 

Scenario 3:

Once the liquid water at the end of scenario 2 melts completely, the scientist turns off the gas and monitors what happens to the water. Despite being in the cold air, the water never freezes.

Scenario 4:

The scientist takes the frozen water from the end of scenario 1, puts it on the active stove, and the water remains frozen.

Which of the following statements is true of scenario 3?

Possible Answers:

It is never spontaneous.

It is spontaneous at all temperatures.

It can be used to drive unfavorable reactions.

It is spontaneous only at high temperatures.

It is spontaneous only at low temperatures.

Correct answer:

It is never spontaneous.

Explanation:

The reaction described in scenario 3 is the persistence of fully liquid water in the face of low temperatures. In other words, the Liquid-Solid Water Phase Change Reaction is far to the left.  As X must be heat, and there is a shortage of heat in the cold air, the reaction would have to be driven to the right via Le Chatlier's Principle. It could never be spontaneous to the left.

Example Question #7 : Gibbs Free Energy

A scientist prepares an experiment to demonstrate the second law of thermodynamics for a chemistry class. In order to conduct the experiment, the scientist brings the class outside in January and gathers a cup of water and a portable stove.

The temperature outside is –10 degrees Celsius. The scientist asks the students to consider the following when answering his questions:

Gibbs Free Energy Formula:

ΔG = ΔH – TΔS 

 

Liquid-Solid Water Phase Change Reaction:

H2O(l) ⇌ H2O(s) + X

The scientist prepares two scenarios. 

Scenario 1:

The scientist buries the cup of water outside in the snow, returns to the classroom with his class for one hour, and the class then checks on the cup. They find that the water has frozen in the cup.

Scenario 2: 

The scientist then places the frozen cup of water on the stove and starts the gas. The class finds that the water melts quickly.

After the water melts, the scientist asks the students to consider two hypothetical scenarios as a thought experiment. 

Scenario 3:

Once the liquid water at the end of scenario 2 melts completely, the scientist turns off the gas and monitors what happens to the water. Despite being in the cold air, the water never freezes.

Scenario 4:

The scientist takes the frozen water from the end of scenario 1, puts it on the active stove, and the water remains frozen.

If a spontaneous reaction is harnessed to do work, how much useful work can the reaction do?

Possible Answers:

Exactly its Gibbs Free Energy value

Spontaneous reactions typically proceed too quickly to do useful work

Greater than its Gibbs Free Energy value, as this value does not consider enthalpy contributions

Less than its Gibbs Free Energy value, as energy some must go to increase the entropy of the universe

Only nonspontaneous reactions coupled to secondary reactions can do useful work

Correct answer:

Exactly its Gibbs Free Energy value

Explanation:

The definition of Gibbs Free Energy is the amount of useful work that a reaction is able to do under defined conditions. It considers the amount of energy that is lost forever to the universe to comply with the Second Law of Thermodynamics.

Example Question #8 : Gibbs Free Energy

ATP stores energy through its ability to lose a phosphate group to form ADP in the following reaction



At body temperature, the thermodynamic values for ATP hydrolysis are as follow.
ΔG = –30kJ/mol
ΔH = –20kJ/mol
ΔS = 34kJ/mol

Glycolysis is an energy-liberating process (ΔG = –218kJ/mol, ΔH = –20 kJ/mol) that is coupled with the conversion of two ADP molecules into two ATP molecules according to the following reaction.

What is the value of ΔG for the reaction below?

Possible Answers:

–278kJ/mol

218kJ/mol

–158kJ/mol

–218kJ/mol

Correct answer:

–158kJ/mol

Explanation:

First, recognize that if ΔG for the formation of ADP is –30 kJ/mol, the ΔG for the formation of ATP must be +30 kJ/mol. Next, we can combine the ΔG of glycolysis with the ΔG of the formation of two ATP molecules (notice the coefficient of 2 in order to balance ATP in the equation).

ΔGglucose = –218kJ/mol
ΔGATP = 30kJ/mol
ΔGtotal = –218 kJ/mol + 2(30kJ/mol) = –158kJ/mol

Example Question #9 : Gibbs Free Energy

For any given chemical reaction, one can draw an energy diagram. Energy diagrams depict the energy levels of the different steps in a reaction, while also indicating the net change in energy and giving clues to relative reaction rate. 

Below, a reaction diagram is shown for a reaction that a scientist is studying in a lab. A student began the reaction the evening before, but the scientist is unsure as to the type of the reaction. He cannot find the student’s notes, except for the reaction diagram below.

 

 

Untitled

Instead of "Energy" on the Y-axis, the graduate student in the passage instead labels the axis "Heat." In this case, what can we say for sure about the reaction in question?

(Note: consider the reaction in the vessel to be the system, and the remainder of the universe as the surroundings)

Possible Answers:

The surroundings must lose entropy

The system must lose entropy

The system may either lose or gain entropy

The system must gain entropy

There is no net entropy change in the system or the surroundings

Correct answer:

The system may either lose or gain entropy

Explanation:

With the change to the chart described in the passage, we know that the system is losing heat from reactants to products (5 is lower than 1). This heat is going out of the system to the surroundings, increasing entropy of the universe. Because of this, the system may either gain or lose entropy.

Any entropy losses in the system, however, must be more than balanced by the entropy gained via heat in the surroundings. The universe (system + surroundings) always has a net gain of entropy. Essentailly, since the value for the surroundings will be positive, the value for the system may be either positive or negative, as long at their sum remains positive.

Example Question #1 : Gibbs Free Energy

Imagine there is an endothermic reaction where entropy is increased in the system. This reaction is not spontaneous at room temperature. What can be done in order to make the reaction spontaneous?

Possible Answers:

Increase the temperature

Decrease the reactant concentrations

Increase the concentration of the products

Add a catalyst

Correct answer:

Increase the temperature

Explanation:

The Gibbs free energy equation is written as .

Since a negative  results in a spontaneous reaction, we can manipulate the variables in order to make the reaction progress. Since entropy is positive in this equation, an increasing temperature will eventually equal the positive enthalpy of the reaction. Once the temperature overtakes the enthalpy, the reaction will be spontaneous. 

In order to be spontaneous, in this case, .

Example Question #11 : Gibbs Free Energy

Imagine the following reaction: .

The reaction has an equilibrium constant of 45.8. The initial concentrations of A, B, and C result in a reaction quotient of 35.6.

Which of the following is true at the beginning of the reaction?

Possible Answers:

Keq and  are both greater than 1

The reaction is not spontaneous

Correct answer:

Explanation:

When a reaction is spontaneous,  is less than 0. Since the reaction quotient (Q) is less than the equilibrium constant (Keq), the reaction will proceed in the forward direction.

Example Question #12 : Gibbs Free Energy

Imagine a galvanic cell which uses solid zinc and aqueous iron ions to produce a voltage.

 

    

     

Based on the above reaction, which of the following statements is false?

Possible Answers:

The reaction is spontaneous

Electrons will travel from the anode to the cathode

Correct answer:

Explanation:

A positive cell potential means that the reaction is spontaneous, and is true of all galvanic cells. This is seen in the equation , where "" is the number of electrons in moles that are transferred in the balanced equation, "" is Faraday's constant, and "" is the cell potential. A positive cell potential results in a negative  meaning the reaction is spontaneous.

A negative  value means that the equilibrium constant for the reaction is greater than 1, while a positive value mean the equilibrium constant is less than 1.

Example Question #11 : Thermochemistry And Energetics

The combustion of liquid hexane in air at 298K gives gaseous carbon dioxide and liquid water, as shown in this reaction.

.

The  for this reaction at 298K is .

At 298K, the  for the above reaction would be __________. At very low temperature, the  would be __________, meaning the reaction would be __________ at very low temperature. Assume  is the same at 298K and at very low temperature.

Possible Answers:

negative . . . negative . . . spontaneous

negative . . . negative . . . non-spontaneous

positive . . . negative . . . spontaneous

negative . . . positive . . . non-spontaneous

positive . . . positive . . . non-spontaneous

Correct answer:

negative . . . negative . . . spontaneous

Explanation:

 for this reaction is negative, because the reactants have nineteen moles of gas while the products have only twelve. Entropy will always decrease in the system if there is a decrease in the number of moles of gas; we know that entropy must be negative for this reaction.

To determine the  at low temperature, use the following formula for Gibbs free energy.

The reaction is exothermic because we are giver that the enthalpy is negative.

 

The entropy, , is also negative, as discussed above.

This makes our equation .

Remember that temperature is given in Kelvin, and will never be negative. At very low temperatures, the  term will be dominant, and will be less than zero, making negative. A negative value for indicates that the reaction will be spontaneous.

Example Question #14 : Gibbs Free Energy

If the overall reaction has a positive change in entropy, which of the following statements about the reaction spontaneity is true?

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Possible Answers:

The reaction is spontaneous at all temperatures

The reaction is spontaneous only at low temperatures

The reaction is spontaneous only at high temperatures

The reaction is spontaneous at room temperature

The reaction is not spontaneous at any temperature

Correct answer:

The reaction is spontaneous at all temperatures

Explanation:

A reaction is spontaneous if the change of Gibbs free energy  is less than zero.

The total reaction is the change .

For this question, the change of enthalpy  is negative, since D is lower in energy than A. There is a net release of energy, making the reaction exothermic. The question states that the change of entropy  is positive, and temperature is always positive when measured in Kelvin. We can return to the Gibbs free energy equation to see the result of these characteristics.

Both terms on the right side are always negative, and  would always be negative. The reaction would be spontaneous at any temperature.

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