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Flashcards in Energy and Entropy Deck (38)
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Spontaneous process?

Those that are started and continue without any outside intervention, move towards their equilibrium state without being driven on by an external influence



Amount of disorder or randomness in a system reflected in the number of ways that the molecules and energy in a system can be arranged


Change in entropy?

Given by the difference between the final and the initial states of the system


Second law of thermodynamics?

Spontaneous processes are those that increase the total entropy of the universe


Total entropy change of a system?

Change of entropy in system + change in entropy of surroundings


When is a process spontaneous?

When the total entropy is greater than 0


When is a process non spontaneous?

When the total entropy is less than 0


When is a process at equilibrium?

When the total entropy is equal to 0


Adding heat reversibly?

Heat is added very slowly so that at any stage the temperature difference between the system and its surroundings is infinitesimally small and so is always close to thermal equilibrium, molecules move around faster chemical bonds vibrate more and higher energy levels are populated, this leads to the system having greater disorder and hence higher energy, adding the same amount of heat has a greater effect at lower temperature than at higher temperature


Entropy changes during changes of phase?

A change of phase is reversible since it takes place at equibrlium at the normal temperature of the phase change the reversible heat change at constant pressure is the enthalpy change so that qrev = enthalpy change


Entropy changes for vaporisation and fusion?

entropy change of vaporisation = entropy of vapour - entropy of liquid
entropy change of fusion = entropy of liquid - entropy solid
They have positive values consistent with idea of entropy and measure of disorder


Entropy changes for reverse process of vaporisation and fusion?

They have the opposite sign but the same value


Entropy and temperature?

As the temperature increases matter generally becomes more disordered, therefore entropy of system increases with increasing temperature.


What does the derivation of the equation for change of entropy with change of temperature assume?

That no phase change occurs within the temperature range so the compound remains in the same state between the two temperatures, equation gives sufficient accuracy over small temperature ranges where cp is the mean value over the range, for greater accuracy the temperature variation of cp must be taken into account


Third law of thermodynamics?

The entropy of a perfect crystal at zoo kelvin is zero, a perfectly ordered system has no disorder or motion of any type so must have zero entropy and since at 0K all molecules are in their ground state there is only one way of arranging the molecules so entropy is zero


Perfect crystal?

One with all the atoms or ions or molecules aligned perfectly and with no defects - in reality this is impossible to achieve since all crystals contain defects


Standard enthalpy change?

Entropy changes on heating 1 mol of a substance from 0K to 298K taking into account any phase changes that occur, sometimes called absolute or third law entropies, provide a convenient way to calculate entropy changes during chemical reactions


To find standard entropy?

Calculate each of the entropy changes at 1 bar in taking 1 mole of the substance through the phase changes, it can also be found using a graphical method with experimental data for Cp and T, finding the area under the curves is equivalent to performing the integrals


How to find standard entropy of reaction?

Sum of entropy of products - sum of entropy of reactants


Spontaneous process and sign of Gibbs energy?

A spontaneous process at constant temperature and pressure has a negative value for the change in Gibbs energy


How can change in Gibbs energy be used to predict spontaneity?

delta G < 0 the reaction is spontaneous
delta G > 0 the reaction is non spontaneous
delta G = 0 the reaction is at equilibrium


Why are processes that have delta G < 0 spontaneous?

They increase the entropy of the universe and thus obey the second law, Gibbs energy gives a convenient way of applying the second law while considering properties only of the system, if a process that is non spontaneous is the forward reaction it will be spontaneous in the reverse reaction


For an endothermic reaction what is the value of enthalpy change, entropy change, change in Gibbs energy at different temperatures and the spontaneity?

change in enthalpy Positive > 0
change in entropy negative < 0
value of Gibbs energy POSITIVE for all T
Never spontaneous

change in enthalpy Positive > 0
change in entropy positive > 0
value of Gibbs energy POSITIVE for LOW T
Becomes spontaneous on heating


For an exothermic reaction what is the value of enthalpy change, entropy change, change in Gibbs energy at different temperatures and the spontaneity?

change in enthalpy negative < 0
change in entropy positive > 0
value of Gibbs energy NEGATIVE for all T
Always spontaneous

change in enthalpy negative < 0
change in entropy negative < 0
value of Gibbs energy POSITIVE for HIGH T
Becomes spontaneous on cooling


Lowering of Gibbs energy?

If a process or reaction results in a lowering of the Gibbs energy it is spontaneous it is favourable and can happen however it does not mean that it will happen, a reaction may be kinetically unfavourable as it has a high activation energy, however once started the reaction will readily go to completion, the Gibbs energy change is useful since if the value of delta G can be calculated for a reaction or process the spontaneity can be predicted


Standard Gibbs energy change of formation?

The change in Gibbs energy when 1 mole of a compound is formed at 1 bar and 298K from its elements in their standard states, compounds have lower Gibbs energies (negative values) than their constituent elements and are therefore more stable with respect to their elements


Gibbs energy change of reaction?

Gibbs energy changes of formation can be used to calculate the change in Gibbs energy driving the reaction
delta G of reaction = sum of Gibbs energy changes of formation of products - sum of Gibbs energy changes of formation of reactants


How can Gibbs energy changes be used for coupled reactions?

Even if a reaction has a positive value of Gibbs energy change of reaction that does not necessarily mean it cannot be used, the reaction in isolation will not be spontaneous but it can be made to occur if it is couple to another reaction with a larger Gibbs energy change of reaction, such reactions are sometimes called tandem reactions


Gibbs energy changes and maximum work?

Gibbs energy changes value is equivalent to the maximum non expansion work that can be obtained from a change, this is the maximum amount of work that the change can do after any work due to change in valued has been accounted for


What is thermodynamic activity used for?

Most chemical reactions occur under non standard conditions at temperatures other than 298K and do not necessarily go to completion. To describe the effects of concentration and pressure a term called the thermodynamic activity is used