MCAT Physical : Physical Chemistry

Study concepts, example questions & explanations for MCAT Physical

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Example Questions

Example Question #42 : Biochemistry, Organic Chemistry, And Other Concepts

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:

Electrons will travel from the anode to the cathode

The reaction is spontaneous

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 : Gibbs Free Energy

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

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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 . . . positive . . . non-spontaneous

positive . . . positive . . . non-spontaneous

negative . . . negative . . . non-spontaneous

positive . . . negative . . . spontaneous

negative . . . negative . . . 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 room temperature

The reaction is not spontaneous at any temperature

The reaction is spontaneous only at low temperatures

The reaction is spontaneous at all temperatures

The reaction is spontaneous only at high temperatures

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.

Example Question #15 : Gibbs Free Energy

Which set of conditions will result in a reaction always being non-spontaneous?

Possible Answers:

A positive  and positive

A negative and positive

A negative and negative 

A positive  and negative 

Equal values for and

Correct answer:

A positive  and negative 

Explanation:

A chemical reaction will be spontaneous when its change in Gibbs free energy, or , is negative. This value can be represented numerically by the equation:

First, let's look at the value for . The equation is more likely to yield a negative  value if this variable is below zero, so we want a negative value for . , however, is being subtracted, so a positive  value will give us a more negative . In combination, these conditions give us a negative value minus a positive one, which will always yield a negative answer.

If a reaction with a negative and a positive is always spontaneous, we can reason that a reaction with a positive and negative can never be spontaneous. This combination will yield a positive value minus a negative value, always resulting in a positive solution.

Example Question #1 : Laws Of Thermodynamics

A student conducts an experiment for a chemistry class. The student wishes to explore power generation from different types of voltaic cells. He sets up three different cells, and then compares the amount of energy generated from each one.

One of his cells is shown below as an example. Both remaining cells follow the same layout.

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A scientist discovers that a voltaic cell he constructs is able to run and produce energy indefinitely, without ever needing intervention again. Which law is this cell violating?

Possible Answers:

The cell is not violating thermodynamics

The third law of thermodynamics

The second law of thermodynamics

The first law of thermodynamics

The zeroth law of thermodynamics

Correct answer:

The first law of thermodynamics

Explanation:

The first law of thermodynamics is the conservation of energy law. A cell that produces energy indefinitely is functionally a perpetual motion machine, and is prohibited by the first law.

Example Question #2 : Laws Of Thermodynamics

A researcher measures the kinetic energy of a chair sliding on a rough floor. At the beginning of motion the chair has a kinetic energy of . Once the chair stops sliding the kinetic energy is . What can you conclude about the researcher’s results?

Possible Answers:

The results are invalid because they violate the second law of thermodynamics

The results do not violate the first law of thermodynamics because energy is not destroyed

The results are invalid because they violate the first law of thermodynamics

The results do not violate the second law of thermodynamics because energy can be destroyed if entropy increases

Correct answer:

The results do not violate the first law of thermodynamics because energy is not destroyed

Explanation:

The first law of thermodynamics states that the energy of the universe is constant because energy cannot be created or destroyed; however, it is possible for energy to be converted from one form to another. In this question the chair has kinetic energy in the beginning, but it loses all of this energy once it stops. This doesn’t mean that the kinetic energy is destroyed; it means that the kinetic energy is converted to another form of energy. Since it is sliding on a floor with a lot of friction (rough floor), the chair converts the kinetic energy to heat.

The second law of thermodynamics states that the entropy of the universe is always increasing. This law is irrelevant to the question.

Example Question #1 : Laws Of Thermodynamics

Which of the following is true of an adiabatic expansion?

Possible Answers:

Temperature decreases

Temperature remains constant

Heat is gained

Temperature increases

Heat is lost

Correct answer:

Temperature decreases

Explanation:

In thermodynamics, no heat is exchanged in an adiabatic process, so heat is neither gained, nor lost. In an adiabatic compression temperature increases, but in an expansion temperature decreases.

Example Question #3 : Laws Of Thermodynamics

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.

The same scientist in the passage measures the variables of another reaction in the lab. He knows that this reaction is spontaneous under standard conditions, with a standard free energy change of –43 kJ/mol. Using laboratory-calculated variables, he determines that the Gibbs Free Energy has a value of 0 kJ/mol. What can we say about this reaction?

Possible Answers:

It indicates that the reaction will produce 43 kJ of energy for every mole that is allowed to react spontaneously under current conditions.

The reaction had reached equilibrium when the scientist made his measurements.

43 kJ of energy must be put into the system to have the reaction proceed spontaneously.

The scientist made an error, all spontaneous reactions have a negative Gibbs Free Energy value.

The reaction will always produce 43 kJ of heat when it reacts to completion.

Correct answer:

The reaction had reached equilibrium when the scientist made his measurements.

Explanation:

A reaction with a zero free energy change is at equilibrium. At standard conditions, not at equilibrium, this reaction would have a Gibbs free energy change of –43 kJ/mol, would be spontaneous, and would be able to produce 43 kJ of useful work for every mole that reacts.

Example Question #1 : Laws Of Thermodynamics

An air conditioning unit is supplied with power to effectively cool an entire house without generating heat.

Which law(s) of thermodynamics is(are) violated?

I. The first law

II. The second law

III. The third law

Possible Answers:

II and III

II only

III only

I and II

I only

Correct answer:

II only

Explanation:

The first law of thermodynamics, conservation of energy, is not violated since the refrigerator is merely transforming electrical energy into work.

The second law of thermodynamics, increase of entropy, is violated since the entropy of a cooled house is lower, but there is no corresponding increase in entropy elsewhere. In order to cool an object in the system, and object in the surroundings must be heated.

The third law of thermodynamics deals with absolute zero and is not relevant.

Example Question #1 : Laws Of Thermodynamics

Consider the following reaction. 

Which of the following is true about this reaction?

Possible Answers:

This reaction is endergonic because the enthalpy change is greater than zero

This reaction increases the entropy of the universe because it is a spontaneous reaction

This reaction is exothermic because the free energy change is less than zero

This reaction increases the entropy of the universe because it is a non-spontaneous reaction

Correct answer:

This reaction increases the entropy of the universe because it is a spontaneous reaction

Explanation:

The question states that the change in Gibbs free energy, , is negative. This means that the reaction is spontaneous. Second law of thermodynamics states that a spontaneous process always increases the entropy of the universe. Note that the second law only addresses the entropy of the universe; the change in entropy of a reaction could be either positive or negative. 

This reaction is exergonic (spontaneous) because the change in Gibbs free energy () is negative. It is also endothermic because the change in enthalpy () is positive.

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