Determination of enthelpy of solution (solubility/temp stuff)

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SUMMARY

This discussion centers on the determination of the enthalpy of solution for benzoic acid in water using the van't Hoff equation. The equation, expressed as lnk = -ΔH/RT + constant, allows for the calculation of enthalpy change from the slope of a graph plotting ln(solubility) against 1/Temp. It is established that solubility does not need to be expressed in mol/L since the difference in solubility is what matters, leading to consistent gradients regardless of units. Additionally, solubility (S) can be used in place of the equilibrium constant (K) in the van't Hoff equation due to their proportional relationship under specific conditions.

PREREQUISITES
  • Understanding of the van't Hoff equation and its application in thermodynamics.
  • Knowledge of solubility concepts and equilibrium constants in chemistry.
  • Familiarity with plotting graphs and interpreting slopes in scientific data.
  • Basic principles of acid-base chemistry, particularly regarding weak acids like benzoic acid.
NEXT STEPS
  • Study the van't Hoff equation in detail, focusing on its derivation and applications in thermodynamics.
  • Research solubility equilibrium and its relationship with equilibrium constants.
  • Explore the concept of enthalpy changes in solution processes, particularly for weak acids.
  • Learn about the graphical representation of thermodynamic data and how to interpret slopes and intercepts.
USEFUL FOR

Chemistry students, researchers in thermodynamics, and professionals involved in solution chemistry will benefit from this discussion, particularly those studying the solubility and enthalpy changes of compounds like benzoic acid.

_Greg_
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Just done an experiment where you dissolve benzoic acid in water at different temperatures and different volumes of water.

From the van't hoff equation you then plot a graph of ln(solubility) against 1/Temp which produces a straight line with gradient -ΔH/RT from which you get the enthalpy change.

(vant hoff equation): lnk = -ΔH/RT + constant

The first question was:

why isn't it necessary to express solubility in mol/l despite ΔH beight evaluated in J/mol?

I answered with:

It isn’t necessary to convert solubility into mol/l because it’s the difference in solubility that’s important. Therefore plotting solubility with either units will always produce a line of the same gradient but with different Y intercept (the intercept being insignificant)

Is that ok?

The second question I am stuck on is:

Why is it that solubility, S, may be used instead of the equilibrium constant, K, in the van't hoff equation?

I would guess they are proportional to each other or something?

would really appreciate any help :smile:
 
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_Greg_ said:
(vant hoff equation): lnk = -ΔH/RT + constant

why isn't it necessary to express solubility in mol/l despite ΔH beight evaluated in J/mol?

I answered with:

It isn’t necessary to convert solubility into mol/l because it’s the difference in solubility that’s important. Therefore plotting solubility with either units will always produce a line of the same gradient but with different Y intercept (the intercept being insignificant)

Is that ok?
I believe you are right. As long as -H/RT is using the correct units, the slope should be the same. Remember that this is only true if the units being used have a direct linear correlation to the other units being used.
Why is it that solubility, S, may be used instead of the equilibrium constant, K, in the van't hoff equation?

I would guess they are proportional to each other or something?
Correct, but you should probably say why that is true. Wikipedia has an explanation of solubility equilibrium. Under nonionic it says this:

If the activity of the substance in solution is constant (i.e. not affected by any other solutes that may be present) it may be replaced by the concentration.

K_s = \left[\mathrm{{C}_{12}{H}_{22}{O}_{11}}(aq)\right]\

The square brackets mean molar concentration in mol dm-3 (sometimes called molarity with symbol M).

This statement says that water at equilibrium with solid sugar contains a concentration equal to K. For table sugar (sucrose) at 25 °C, K = 1.971 mol/L.
Remember that this is only true because benzoic acid is a weak acid meaning the majority of it is COOH (which applies to the above quote). Only a tiny fraction of it is the ionic COO- form, to which Ka applies, but it's so small you can probably just ignore it.

edit: Firefox actually copies tex code from wikipedia. Fascinating.
 
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