Why is my conclusion inconsistent with the van't Hoff equation?
$begingroup$
Let's say I hypothesize that a graph of $ln K$ vs. $1/T$ has a slope of $-∆G^circ/R$ and a $y$-intercept of $0$. I prove it simply:
$$∆G^circ = -RTln K quadtoquad ln K = -frac{∆G^circ}{RT}$$
This matches the linear form $y = mx + b$. Thus, plotting $ln K$ vs. $1/T$ would have a slope $m = -∆G^circ/R$ and a $y$-intercept $b = 0$.
However, I understand that a van't Hoff plot defines a graph of $ln K$ vs. $1/T$ to have a slope of $-ΔH^circ/R$ and a $y$-intercept of $∆S^circ/R$. It is clear from the relation $∆G^circ = ∆H^circ - TΔS^circ$ that my final equation is thermodynamically equivalent to the van't Hoff equation. I do not disagree that
$$ln K = -frac{∆H^circ}{RT} + frac{∆S^circ}{R},$$
but if I were to experimentally measure temperature and calculate the equilibrium constant temperature, why should I expect the y-intercept to be $∆S^circ/R$ as defined by van't Hoff rather than $0$ as I defined above? Why should I expect the slope to be $-ΔH^circ/R$ instead of $-ΔG^circ/R$? What makes the van't Hoff equation match experimentally determined values over the equation $ln K = -∆G^circ/(RT)$?
thermodynamics free-energy
New contributor
Mateen Kasim is a new contributor to this site. Take care in asking for clarification, commenting, and answering.
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$endgroup$
add a comment |
$begingroup$
Let's say I hypothesize that a graph of $ln K$ vs. $1/T$ has a slope of $-∆G^circ/R$ and a $y$-intercept of $0$. I prove it simply:
$$∆G^circ = -RTln K quadtoquad ln K = -frac{∆G^circ}{RT}$$
This matches the linear form $y = mx + b$. Thus, plotting $ln K$ vs. $1/T$ would have a slope $m = -∆G^circ/R$ and a $y$-intercept $b = 0$.
However, I understand that a van't Hoff plot defines a graph of $ln K$ vs. $1/T$ to have a slope of $-ΔH^circ/R$ and a $y$-intercept of $∆S^circ/R$. It is clear from the relation $∆G^circ = ∆H^circ - TΔS^circ$ that my final equation is thermodynamically equivalent to the van't Hoff equation. I do not disagree that
$$ln K = -frac{∆H^circ}{RT} + frac{∆S^circ}{R},$$
but if I were to experimentally measure temperature and calculate the equilibrium constant temperature, why should I expect the y-intercept to be $∆S^circ/R$ as defined by van't Hoff rather than $0$ as I defined above? Why should I expect the slope to be $-ΔH^circ/R$ instead of $-ΔG^circ/R$? What makes the van't Hoff equation match experimentally determined values over the equation $ln K = -∆G^circ/(RT)$?
thermodynamics free-energy
New contributor
Mateen Kasim is a new contributor to this site. Take care in asking for clarification, commenting, and answering.
Check out our Code of Conduct.
$endgroup$
add a comment |
$begingroup$
Let's say I hypothesize that a graph of $ln K$ vs. $1/T$ has a slope of $-∆G^circ/R$ and a $y$-intercept of $0$. I prove it simply:
$$∆G^circ = -RTln K quadtoquad ln K = -frac{∆G^circ}{RT}$$
This matches the linear form $y = mx + b$. Thus, plotting $ln K$ vs. $1/T$ would have a slope $m = -∆G^circ/R$ and a $y$-intercept $b = 0$.
However, I understand that a van't Hoff plot defines a graph of $ln K$ vs. $1/T$ to have a slope of $-ΔH^circ/R$ and a $y$-intercept of $∆S^circ/R$. It is clear from the relation $∆G^circ = ∆H^circ - TΔS^circ$ that my final equation is thermodynamically equivalent to the van't Hoff equation. I do not disagree that
$$ln K = -frac{∆H^circ}{RT} + frac{∆S^circ}{R},$$
but if I were to experimentally measure temperature and calculate the equilibrium constant temperature, why should I expect the y-intercept to be $∆S^circ/R$ as defined by van't Hoff rather than $0$ as I defined above? Why should I expect the slope to be $-ΔH^circ/R$ instead of $-ΔG^circ/R$? What makes the van't Hoff equation match experimentally determined values over the equation $ln K = -∆G^circ/(RT)$?
thermodynamics free-energy
New contributor
Mateen Kasim is a new contributor to this site. Take care in asking for clarification, commenting, and answering.
Check out our Code of Conduct.
$endgroup$
Let's say I hypothesize that a graph of $ln K$ vs. $1/T$ has a slope of $-∆G^circ/R$ and a $y$-intercept of $0$. I prove it simply:
$$∆G^circ = -RTln K quadtoquad ln K = -frac{∆G^circ}{RT}$$
This matches the linear form $y = mx + b$. Thus, plotting $ln K$ vs. $1/T$ would have a slope $m = -∆G^circ/R$ and a $y$-intercept $b = 0$.
However, I understand that a van't Hoff plot defines a graph of $ln K$ vs. $1/T$ to have a slope of $-ΔH^circ/R$ and a $y$-intercept of $∆S^circ/R$. It is clear from the relation $∆G^circ = ∆H^circ - TΔS^circ$ that my final equation is thermodynamically equivalent to the van't Hoff equation. I do not disagree that
$$ln K = -frac{∆H^circ}{RT} + frac{∆S^circ}{R},$$
but if I were to experimentally measure temperature and calculate the equilibrium constant temperature, why should I expect the y-intercept to be $∆S^circ/R$ as defined by van't Hoff rather than $0$ as I defined above? Why should I expect the slope to be $-ΔH^circ/R$ instead of $-ΔG^circ/R$? What makes the van't Hoff equation match experimentally determined values over the equation $ln K = -∆G^circ/(RT)$?
thermodynamics free-energy
thermodynamics free-energy
New contributor
Mateen Kasim is a new contributor to this site. Take care in asking for clarification, commenting, and answering.
Check out our Code of Conduct.
New contributor
Mateen Kasim is a new contributor to this site. Take care in asking for clarification, commenting, and answering.
Check out our Code of Conduct.
edited 3 hours ago
Karsten Theis
4,564542
4,564542
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asked 6 hours ago
Mateen KasimMateen Kasim
192
192
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add a comment |
add a comment |
2 Answers
2
active
oldest
votes
$begingroup$
In the linear form $y = mx + b$, both $m$ and $b$ are constants, i.e. they don't depend on $x$. On the other hand, $Delta G^circ$ definitely depends on the temperature (and consequently on its inverse $1/T$). So if you plot a function $$f(x) = m x$$ where $m$ is not a constant but a function dependent on $x$, you might get something unexpected. In your case, $x$ is $1/T$ and $$m = -frac{Delta H}{R} + frac{T Delta S}{R}$$
The $y$-intercept corresponds to an infinitely high temperature where $-frac{Delta H}{R} times frac{1}{T}$ tends to zero and $frac{T Delta S}{R} times frac{1}{T}$ cancels to be just $frac{Delta S}{R}$.
$endgroup$
$begingroup$
Isn't ∆Gº a constant defined at 298 K? The relation ∆Gº=-RTlnK gives the standard change in free energy (i.e. 298 K, 100 kPa, 1M), so wouldn't this value be constant for a given reaction? Plus, if we were talking about non-standard values, doesn't change in enthalpy depend on temperature as well?
$endgroup$
– Mateen Kasim
1 hour ago
1
$begingroup$
@MateenKasim You are varying the temperature. The Gibbs energy and the equilibrium constant are significantly temperature-dependent. The enthalpy is temperature-dependent too, but to a much lesser degree.
$endgroup$
– Karsten Theis
34 mins ago
add a comment |
$begingroup$
The fact of the matter is that the differential version of your equation
$$frac{mathrm{d}ln{K}}{mathrm{d}left(frac{1}{T}right)} = -frac{Delta G^circ}{R}$$
is not exact (because $Delta G^circ$ is a function of $T$) while the form of the van't Hoff equation involving differentials
$$frac{mathrm{d}ln{K}}{mathrm{d}left(frac{1}{T}right)} = -frac{Delta H^circ}{R}$$
is exact. Moreover, the derivation of the van't Hoff equation properly takes into account the fact that, in varying temperature $T$, the initial and final states for $Delta G^circ$ are constrained to be at 1 bar. So, in the van't Hoff development, the temperature derivative of $Delta G^circ$ is exactly given by
$$frac{Delta G^circ}{mathrm{d}T} = -Delta S^circ$$
This important constraint is not even addressed in your approach.
Finally, do you have a reference where it asserts that the intercept at $(1/T) to 0$ is supposed to be $Delta S^circ/R$?
$endgroup$
add a comment |
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2 Answers
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active
oldest
votes
2 Answers
2
active
oldest
votes
active
oldest
votes
active
oldest
votes
$begingroup$
In the linear form $y = mx + b$, both $m$ and $b$ are constants, i.e. they don't depend on $x$. On the other hand, $Delta G^circ$ definitely depends on the temperature (and consequently on its inverse $1/T$). So if you plot a function $$f(x) = m x$$ where $m$ is not a constant but a function dependent on $x$, you might get something unexpected. In your case, $x$ is $1/T$ and $$m = -frac{Delta H}{R} + frac{T Delta S}{R}$$
The $y$-intercept corresponds to an infinitely high temperature where $-frac{Delta H}{R} times frac{1}{T}$ tends to zero and $frac{T Delta S}{R} times frac{1}{T}$ cancels to be just $frac{Delta S}{R}$.
$endgroup$
$begingroup$
Isn't ∆Gº a constant defined at 298 K? The relation ∆Gº=-RTlnK gives the standard change in free energy (i.e. 298 K, 100 kPa, 1M), so wouldn't this value be constant for a given reaction? Plus, if we were talking about non-standard values, doesn't change in enthalpy depend on temperature as well?
$endgroup$
– Mateen Kasim
1 hour ago
1
$begingroup$
@MateenKasim You are varying the temperature. The Gibbs energy and the equilibrium constant are significantly temperature-dependent. The enthalpy is temperature-dependent too, but to a much lesser degree.
$endgroup$
– Karsten Theis
34 mins ago
add a comment |
$begingroup$
In the linear form $y = mx + b$, both $m$ and $b$ are constants, i.e. they don't depend on $x$. On the other hand, $Delta G^circ$ definitely depends on the temperature (and consequently on its inverse $1/T$). So if you plot a function $$f(x) = m x$$ where $m$ is not a constant but a function dependent on $x$, you might get something unexpected. In your case, $x$ is $1/T$ and $$m = -frac{Delta H}{R} + frac{T Delta S}{R}$$
The $y$-intercept corresponds to an infinitely high temperature where $-frac{Delta H}{R} times frac{1}{T}$ tends to zero and $frac{T Delta S}{R} times frac{1}{T}$ cancels to be just $frac{Delta S}{R}$.
$endgroup$
$begingroup$
Isn't ∆Gº a constant defined at 298 K? The relation ∆Gº=-RTlnK gives the standard change in free energy (i.e. 298 K, 100 kPa, 1M), so wouldn't this value be constant for a given reaction? Plus, if we were talking about non-standard values, doesn't change in enthalpy depend on temperature as well?
$endgroup$
– Mateen Kasim
1 hour ago
1
$begingroup$
@MateenKasim You are varying the temperature. The Gibbs energy and the equilibrium constant are significantly temperature-dependent. The enthalpy is temperature-dependent too, but to a much lesser degree.
$endgroup$
– Karsten Theis
34 mins ago
add a comment |
$begingroup$
In the linear form $y = mx + b$, both $m$ and $b$ are constants, i.e. they don't depend on $x$. On the other hand, $Delta G^circ$ definitely depends on the temperature (and consequently on its inverse $1/T$). So if you plot a function $$f(x) = m x$$ where $m$ is not a constant but a function dependent on $x$, you might get something unexpected. In your case, $x$ is $1/T$ and $$m = -frac{Delta H}{R} + frac{T Delta S}{R}$$
The $y$-intercept corresponds to an infinitely high temperature where $-frac{Delta H}{R} times frac{1}{T}$ tends to zero and $frac{T Delta S}{R} times frac{1}{T}$ cancels to be just $frac{Delta S}{R}$.
$endgroup$
In the linear form $y = mx + b$, both $m$ and $b$ are constants, i.e. they don't depend on $x$. On the other hand, $Delta G^circ$ definitely depends on the temperature (and consequently on its inverse $1/T$). So if you plot a function $$f(x) = m x$$ where $m$ is not a constant but a function dependent on $x$, you might get something unexpected. In your case, $x$ is $1/T$ and $$m = -frac{Delta H}{R} + frac{T Delta S}{R}$$
The $y$-intercept corresponds to an infinitely high temperature where $-frac{Delta H}{R} times frac{1}{T}$ tends to zero and $frac{T Delta S}{R} times frac{1}{T}$ cancels to be just $frac{Delta S}{R}$.
edited 3 hours ago
answered 5 hours ago
Karsten TheisKarsten Theis
4,564542
4,564542
$begingroup$
Isn't ∆Gº a constant defined at 298 K? The relation ∆Gº=-RTlnK gives the standard change in free energy (i.e. 298 K, 100 kPa, 1M), so wouldn't this value be constant for a given reaction? Plus, if we were talking about non-standard values, doesn't change in enthalpy depend on temperature as well?
$endgroup$
– Mateen Kasim
1 hour ago
1
$begingroup$
@MateenKasim You are varying the temperature. The Gibbs energy and the equilibrium constant are significantly temperature-dependent. The enthalpy is temperature-dependent too, but to a much lesser degree.
$endgroup$
– Karsten Theis
34 mins ago
add a comment |
$begingroup$
Isn't ∆Gº a constant defined at 298 K? The relation ∆Gº=-RTlnK gives the standard change in free energy (i.e. 298 K, 100 kPa, 1M), so wouldn't this value be constant for a given reaction? Plus, if we were talking about non-standard values, doesn't change in enthalpy depend on temperature as well?
$endgroup$
– Mateen Kasim
1 hour ago
1
$begingroup$
@MateenKasim You are varying the temperature. The Gibbs energy and the equilibrium constant are significantly temperature-dependent. The enthalpy is temperature-dependent too, but to a much lesser degree.
$endgroup$
– Karsten Theis
34 mins ago
$begingroup$
Isn't ∆Gº a constant defined at 298 K? The relation ∆Gº=-RTlnK gives the standard change in free energy (i.e. 298 K, 100 kPa, 1M), so wouldn't this value be constant for a given reaction? Plus, if we were talking about non-standard values, doesn't change in enthalpy depend on temperature as well?
$endgroup$
– Mateen Kasim
1 hour ago
$begingroup$
Isn't ∆Gº a constant defined at 298 K? The relation ∆Gº=-RTlnK gives the standard change in free energy (i.e. 298 K, 100 kPa, 1M), so wouldn't this value be constant for a given reaction? Plus, if we were talking about non-standard values, doesn't change in enthalpy depend on temperature as well?
$endgroup$
– Mateen Kasim
1 hour ago
1
1
$begingroup$
@MateenKasim You are varying the temperature. The Gibbs energy and the equilibrium constant are significantly temperature-dependent. The enthalpy is temperature-dependent too, but to a much lesser degree.
$endgroup$
– Karsten Theis
34 mins ago
$begingroup$
@MateenKasim You are varying the temperature. The Gibbs energy and the equilibrium constant are significantly temperature-dependent. The enthalpy is temperature-dependent too, but to a much lesser degree.
$endgroup$
– Karsten Theis
34 mins ago
add a comment |
$begingroup$
The fact of the matter is that the differential version of your equation
$$frac{mathrm{d}ln{K}}{mathrm{d}left(frac{1}{T}right)} = -frac{Delta G^circ}{R}$$
is not exact (because $Delta G^circ$ is a function of $T$) while the form of the van't Hoff equation involving differentials
$$frac{mathrm{d}ln{K}}{mathrm{d}left(frac{1}{T}right)} = -frac{Delta H^circ}{R}$$
is exact. Moreover, the derivation of the van't Hoff equation properly takes into account the fact that, in varying temperature $T$, the initial and final states for $Delta G^circ$ are constrained to be at 1 bar. So, in the van't Hoff development, the temperature derivative of $Delta G^circ$ is exactly given by
$$frac{Delta G^circ}{mathrm{d}T} = -Delta S^circ$$
This important constraint is not even addressed in your approach.
Finally, do you have a reference where it asserts that the intercept at $(1/T) to 0$ is supposed to be $Delta S^circ/R$?
$endgroup$
add a comment |
$begingroup$
The fact of the matter is that the differential version of your equation
$$frac{mathrm{d}ln{K}}{mathrm{d}left(frac{1}{T}right)} = -frac{Delta G^circ}{R}$$
is not exact (because $Delta G^circ$ is a function of $T$) while the form of the van't Hoff equation involving differentials
$$frac{mathrm{d}ln{K}}{mathrm{d}left(frac{1}{T}right)} = -frac{Delta H^circ}{R}$$
is exact. Moreover, the derivation of the van't Hoff equation properly takes into account the fact that, in varying temperature $T$, the initial and final states for $Delta G^circ$ are constrained to be at 1 bar. So, in the van't Hoff development, the temperature derivative of $Delta G^circ$ is exactly given by
$$frac{Delta G^circ}{mathrm{d}T} = -Delta S^circ$$
This important constraint is not even addressed in your approach.
Finally, do you have a reference where it asserts that the intercept at $(1/T) to 0$ is supposed to be $Delta S^circ/R$?
$endgroup$
add a comment |
$begingroup$
The fact of the matter is that the differential version of your equation
$$frac{mathrm{d}ln{K}}{mathrm{d}left(frac{1}{T}right)} = -frac{Delta G^circ}{R}$$
is not exact (because $Delta G^circ$ is a function of $T$) while the form of the van't Hoff equation involving differentials
$$frac{mathrm{d}ln{K}}{mathrm{d}left(frac{1}{T}right)} = -frac{Delta H^circ}{R}$$
is exact. Moreover, the derivation of the van't Hoff equation properly takes into account the fact that, in varying temperature $T$, the initial and final states for $Delta G^circ$ are constrained to be at 1 bar. So, in the van't Hoff development, the temperature derivative of $Delta G^circ$ is exactly given by
$$frac{Delta G^circ}{mathrm{d}T} = -Delta S^circ$$
This important constraint is not even addressed in your approach.
Finally, do you have a reference where it asserts that the intercept at $(1/T) to 0$ is supposed to be $Delta S^circ/R$?
$endgroup$
The fact of the matter is that the differential version of your equation
$$frac{mathrm{d}ln{K}}{mathrm{d}left(frac{1}{T}right)} = -frac{Delta G^circ}{R}$$
is not exact (because $Delta G^circ$ is a function of $T$) while the form of the van't Hoff equation involving differentials
$$frac{mathrm{d}ln{K}}{mathrm{d}left(frac{1}{T}right)} = -frac{Delta H^circ}{R}$$
is exact. Moreover, the derivation of the van't Hoff equation properly takes into account the fact that, in varying temperature $T$, the initial and final states for $Delta G^circ$ are constrained to be at 1 bar. So, in the van't Hoff development, the temperature derivative of $Delta G^circ$ is exactly given by
$$frac{Delta G^circ}{mathrm{d}T} = -Delta S^circ$$
This important constraint is not even addressed in your approach.
Finally, do you have a reference where it asserts that the intercept at $(1/T) to 0$ is supposed to be $Delta S^circ/R$?
edited 17 mins ago
andselisk
19.6k665127
19.6k665127
answered 37 mins ago
Chet MillerChet Miller
6,6311613
6,6311613
add a comment |
add a comment |
Mateen Kasim is a new contributor. Be nice, and check out our Code of Conduct.
Mateen Kasim is a new contributor. Be nice, and check out our Code of Conduct.
Mateen Kasim is a new contributor. Be nice, and check out our Code of Conduct.
Mateen Kasim is a new contributor. Be nice, and check out our Code of Conduct.
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