proportionality between Gibbs free energy and number of particles
Clash Royale CLAN TAG#URR8PPP
We have the thermodynamic identity for the Gibbs free energy (for a pure system):
$$
dG=-SdT+VdP+mu dN.
$$
Now if we keep $T$ and $P$ fixed, we get
$$
mu=left(fracpartial Gpartial Nright)_T,P.
$$
Using the argument that $T,P$ are intensive quantities (which we keep fixed), while $G$ is extensive, if follows that $Delta G=muDelta N$. However, my book actually claims that
$$
G=mu N.
$$
Now, to me this seems odd, because $G$ still depends on $S,T,V,P$. I know that we're assuming that $T$ and $P$ are fixed, but I would think that we have
$$
G=mu N+x,
$$
where $x$ is some function of $S,T,V,P$. Why isn't this the case? I would think that we can't just set this $x$ to zero for every system, because that way we wouldn't be able to compare two systems where this $x$ would technically be different? Or can it be set to zero, and why?
Here is the relevant text from my book:
EDIT
Hm, so I just looked at this question:
Prove that $G=mu N$ and independance of $mu$ on $N$
It seems then that it's $mu$ which depends on $T,P$, and we're using the fact that $G$ is an extensive quantity. I guess that makes sense. What I do wonder about it how we know that the density stays fixed? Because that's what we need too. So I'm basically confused about the relation
$$
G(T,P,alpha N)=alpha G(T,P,N),
$$
which should be the mathematical phrasing that $G$ is extensive. However, I don't understand why we can "forget" about the volume? We'd still need that
$$
rho=N/V=textconstant. (1)
$$
Where can we find the guarantee that this is the case, and why isn't it expressed in (1)?
thermodynamics
add a comment |
We have the thermodynamic identity for the Gibbs free energy (for a pure system):
$$
dG=-SdT+VdP+mu dN.
$$
Now if we keep $T$ and $P$ fixed, we get
$$
mu=left(fracpartial Gpartial Nright)_T,P.
$$
Using the argument that $T,P$ are intensive quantities (which we keep fixed), while $G$ is extensive, if follows that $Delta G=muDelta N$. However, my book actually claims that
$$
G=mu N.
$$
Now, to me this seems odd, because $G$ still depends on $S,T,V,P$. I know that we're assuming that $T$ and $P$ are fixed, but I would think that we have
$$
G=mu N+x,
$$
where $x$ is some function of $S,T,V,P$. Why isn't this the case? I would think that we can't just set this $x$ to zero for every system, because that way we wouldn't be able to compare two systems where this $x$ would technically be different? Or can it be set to zero, and why?
Here is the relevant text from my book:
EDIT
Hm, so I just looked at this question:
Prove that $G=mu N$ and independance of $mu$ on $N$
It seems then that it's $mu$ which depends on $T,P$, and we're using the fact that $G$ is an extensive quantity. I guess that makes sense. What I do wonder about it how we know that the density stays fixed? Because that's what we need too. So I'm basically confused about the relation
$$
G(T,P,alpha N)=alpha G(T,P,N),
$$
which should be the mathematical phrasing that $G$ is extensive. However, I don't understand why we can "forget" about the volume? We'd still need that
$$
rho=N/V=textconstant. (1)
$$
Where can we find the guarantee that this is the case, and why isn't it expressed in (1)?
thermodynamics
How can your substance have free energy if there are no molecules present? (N=0)
– Chester Miller
Dec 11 at 12:58
@ChesterMiller That's also a fair point.
– Sha Vuklia
Dec 11 at 12:58
add a comment |
We have the thermodynamic identity for the Gibbs free energy (for a pure system):
$$
dG=-SdT+VdP+mu dN.
$$
Now if we keep $T$ and $P$ fixed, we get
$$
mu=left(fracpartial Gpartial Nright)_T,P.
$$
Using the argument that $T,P$ are intensive quantities (which we keep fixed), while $G$ is extensive, if follows that $Delta G=muDelta N$. However, my book actually claims that
$$
G=mu N.
$$
Now, to me this seems odd, because $G$ still depends on $S,T,V,P$. I know that we're assuming that $T$ and $P$ are fixed, but I would think that we have
$$
G=mu N+x,
$$
where $x$ is some function of $S,T,V,P$. Why isn't this the case? I would think that we can't just set this $x$ to zero for every system, because that way we wouldn't be able to compare two systems where this $x$ would technically be different? Or can it be set to zero, and why?
Here is the relevant text from my book:
EDIT
Hm, so I just looked at this question:
Prove that $G=mu N$ and independance of $mu$ on $N$
It seems then that it's $mu$ which depends on $T,P$, and we're using the fact that $G$ is an extensive quantity. I guess that makes sense. What I do wonder about it how we know that the density stays fixed? Because that's what we need too. So I'm basically confused about the relation
$$
G(T,P,alpha N)=alpha G(T,P,N),
$$
which should be the mathematical phrasing that $G$ is extensive. However, I don't understand why we can "forget" about the volume? We'd still need that
$$
rho=N/V=textconstant. (1)
$$
Where can we find the guarantee that this is the case, and why isn't it expressed in (1)?
thermodynamics
We have the thermodynamic identity for the Gibbs free energy (for a pure system):
$$
dG=-SdT+VdP+mu dN.
$$
Now if we keep $T$ and $P$ fixed, we get
$$
mu=left(fracpartial Gpartial Nright)_T,P.
$$
Using the argument that $T,P$ are intensive quantities (which we keep fixed), while $G$ is extensive, if follows that $Delta G=muDelta N$. However, my book actually claims that
$$
G=mu N.
$$
Now, to me this seems odd, because $G$ still depends on $S,T,V,P$. I know that we're assuming that $T$ and $P$ are fixed, but I would think that we have
$$
G=mu N+x,
$$
where $x$ is some function of $S,T,V,P$. Why isn't this the case? I would think that we can't just set this $x$ to zero for every system, because that way we wouldn't be able to compare two systems where this $x$ would technically be different? Or can it be set to zero, and why?
Here is the relevant text from my book:
EDIT
Hm, so I just looked at this question:
Prove that $G=mu N$ and independance of $mu$ on $N$
It seems then that it's $mu$ which depends on $T,P$, and we're using the fact that $G$ is an extensive quantity. I guess that makes sense. What I do wonder about it how we know that the density stays fixed? Because that's what we need too. So I'm basically confused about the relation
$$
G(T,P,alpha N)=alpha G(T,P,N),
$$
which should be the mathematical phrasing that $G$ is extensive. However, I don't understand why we can "forget" about the volume? We'd still need that
$$
rho=N/V=textconstant. (1)
$$
Where can we find the guarantee that this is the case, and why isn't it expressed in (1)?
thermodynamics
thermodynamics
edited Dec 11 at 12:35
asked Dec 11 at 11:49
Sha Vuklia
477216
477216
How can your substance have free energy if there are no molecules present? (N=0)
– Chester Miller
Dec 11 at 12:58
@ChesterMiller That's also a fair point.
– Sha Vuklia
Dec 11 at 12:58
add a comment |
How can your substance have free energy if there are no molecules present? (N=0)
– Chester Miller
Dec 11 at 12:58
@ChesterMiller That's also a fair point.
– Sha Vuklia
Dec 11 at 12:58
How can your substance have free energy if there are no molecules present? (N=0)
– Chester Miller
Dec 11 at 12:58
How can your substance have free energy if there are no molecules present? (N=0)
– Chester Miller
Dec 11 at 12:58
@ChesterMiller That's also a fair point.
– Sha Vuklia
Dec 11 at 12:58
@ChesterMiller That's also a fair point.
– Sha Vuklia
Dec 11 at 12:58
add a comment |
2 Answers
2
active
oldest
votes
Any thermodynamic system has an equation of state, which in this case is of the form $f(P,V,T,N)=0$. Fixing $T$ and $P$ means that $V$ is completely determined by $N$.
The only way this reasoning would fail is if there was an equation of state that didn't involve the volume at all. I have never seen a physical system that had such an equation of state, and I strongly suspect such a system would be unphysical.
Ah, that's genious. Thanks:)
– Sha Vuklia
Dec 11 at 12:51
Oh, and $V$ is usually (if not always) proportional to $N$, so $rho$ will always be fixed.
– Sha Vuklia
Dec 11 at 12:53
add a comment |
The question contains a very common confusion about which independent variables a thermodynamic potential depends on.
$G$ is not a function of $S,T,V,P$. Actually the natural independent variables $G$ depends on can be obtained just looking at the differential: they are $T,P,N$. Each coefficient of the differential form $dG$ should be intended as a function of $T,P,N$, for a fluid one-component system.
Therefore, one would expect to have $mu=mu(P,T,N)$. However, for a normal thermodynamic system, thermodynamic potentials are expected to be extensive, i.e., in this context, $G$ is expected to be a homogeneous function of degree one of its extensive argument $N$. Formally,
$$
G(T,P,alpha N) = alpha G(T,P,N)
$$
should hold for all positive values of $alpha$.
Thus, its is enough to take $alpha=1/N$ (allowed since $N>0$) to get
$$
G(T,P,1) = fracG(T,P,N)N
$$
i.e. $ G(T,P,N) = N G(T,P,1) $, where $ G(T,P,1) $ has no dependence on N.
On the other hand, $mu = left.fracpartialGpartialNright|_T,P$, and we arrive to the conclusion, since: $mu=G(T,P,1)$ is clearly independent on $N$.
This derivation makes clear that a key ingredient to get the result is the extensiveness of the Gibbs free energy, which is granted for large (macroscopic) thermodynamic systems, but could fail for finite systems made by a small number of particles.
Oh, that's so exactly what I needed. I'll keep the other answer as the "accepted one" (as it answered my edited question) - but many, many thanks for the insights you provided, and +1 of course!
– Sha Vuklia
Dec 11 at 17:56
add a comment |
Your Answer
StackExchange.ifUsing("editor", function ()
return StackExchange.using("mathjaxEditing", function ()
StackExchange.MarkdownEditor.creationCallbacks.add(function (editor, postfix)
StackExchange.mathjaxEditing.prepareWmdForMathJax(editor, postfix, [["$", "$"], ["\\(","\\)"]]);
);
);
, "mathjax-editing");
StackExchange.ready(function()
var channelOptions =
tags: "".split(" "),
id: "151"
;
initTagRenderer("".split(" "), "".split(" "), channelOptions);
StackExchange.using("externalEditor", function()
// Have to fire editor after snippets, if snippets enabled
if (StackExchange.settings.snippets.snippetsEnabled)
StackExchange.using("snippets", function()
createEditor();
);
else
createEditor();
);
function createEditor()
StackExchange.prepareEditor(
heartbeatType: 'answer',
autoActivateHeartbeat: false,
convertImagesToLinks: false,
noModals: true,
showLowRepImageUploadWarning: true,
reputationToPostImages: null,
bindNavPrevention: true,
postfix: "",
imageUploader:
brandingHtml: "Powered by u003ca class="icon-imgur-white" href="https://imgur.com/"u003eu003c/au003e",
contentPolicyHtml: "User contributions licensed under u003ca href="https://creativecommons.org/licenses/by-sa/3.0/"u003ecc by-sa 3.0 with attribution requiredu003c/au003e u003ca href="https://stackoverflow.com/legal/content-policy"u003e(content policy)u003c/au003e",
allowUrls: true
,
noCode: true, onDemand: true,
discardSelector: ".discard-answer"
,immediatelyShowMarkdownHelp:true
);
);
Sign up or log in
StackExchange.ready(function ()
StackExchange.helpers.onClickDraftSave('#login-link');
);
Sign up using Google
Sign up using Facebook
Sign up using Email and Password
Post as a guest
Required, but never shown
StackExchange.ready(
function ()
StackExchange.openid.initPostLogin('.new-post-login', 'https%3a%2f%2fphysics.stackexchange.com%2fquestions%2f446602%2fproportionality-between-gibbs-free-energy-and-number-of-particles%23new-answer', 'question_page');
);
Post as a guest
Required, but never shown
2 Answers
2
active
oldest
votes
2 Answers
2
active
oldest
votes
active
oldest
votes
active
oldest
votes
Any thermodynamic system has an equation of state, which in this case is of the form $f(P,V,T,N)=0$. Fixing $T$ and $P$ means that $V$ is completely determined by $N$.
The only way this reasoning would fail is if there was an equation of state that didn't involve the volume at all. I have never seen a physical system that had such an equation of state, and I strongly suspect such a system would be unphysical.
Ah, that's genious. Thanks:)
– Sha Vuklia
Dec 11 at 12:51
Oh, and $V$ is usually (if not always) proportional to $N$, so $rho$ will always be fixed.
– Sha Vuklia
Dec 11 at 12:53
add a comment |
Any thermodynamic system has an equation of state, which in this case is of the form $f(P,V,T,N)=0$. Fixing $T$ and $P$ means that $V$ is completely determined by $N$.
The only way this reasoning would fail is if there was an equation of state that didn't involve the volume at all. I have never seen a physical system that had such an equation of state, and I strongly suspect such a system would be unphysical.
Ah, that's genious. Thanks:)
– Sha Vuklia
Dec 11 at 12:51
Oh, and $V$ is usually (if not always) proportional to $N$, so $rho$ will always be fixed.
– Sha Vuklia
Dec 11 at 12:53
add a comment |
Any thermodynamic system has an equation of state, which in this case is of the form $f(P,V,T,N)=0$. Fixing $T$ and $P$ means that $V$ is completely determined by $N$.
The only way this reasoning would fail is if there was an equation of state that didn't involve the volume at all. I have never seen a physical system that had such an equation of state, and I strongly suspect such a system would be unphysical.
Any thermodynamic system has an equation of state, which in this case is of the form $f(P,V,T,N)=0$. Fixing $T$ and $P$ means that $V$ is completely determined by $N$.
The only way this reasoning would fail is if there was an equation of state that didn't involve the volume at all. I have never seen a physical system that had such an equation of state, and I strongly suspect such a system would be unphysical.
answered Dec 11 at 12:45
probably_someone
16.3k12655
16.3k12655
Ah, that's genious. Thanks:)
– Sha Vuklia
Dec 11 at 12:51
Oh, and $V$ is usually (if not always) proportional to $N$, so $rho$ will always be fixed.
– Sha Vuklia
Dec 11 at 12:53
add a comment |
Ah, that's genious. Thanks:)
– Sha Vuklia
Dec 11 at 12:51
Oh, and $V$ is usually (if not always) proportional to $N$, so $rho$ will always be fixed.
– Sha Vuklia
Dec 11 at 12:53
Ah, that's genious. Thanks:)
– Sha Vuklia
Dec 11 at 12:51
Ah, that's genious. Thanks:)
– Sha Vuklia
Dec 11 at 12:51
Oh, and $V$ is usually (if not always) proportional to $N$, so $rho$ will always be fixed.
– Sha Vuklia
Dec 11 at 12:53
Oh, and $V$ is usually (if not always) proportional to $N$, so $rho$ will always be fixed.
– Sha Vuklia
Dec 11 at 12:53
add a comment |
The question contains a very common confusion about which independent variables a thermodynamic potential depends on.
$G$ is not a function of $S,T,V,P$. Actually the natural independent variables $G$ depends on can be obtained just looking at the differential: they are $T,P,N$. Each coefficient of the differential form $dG$ should be intended as a function of $T,P,N$, for a fluid one-component system.
Therefore, one would expect to have $mu=mu(P,T,N)$. However, for a normal thermodynamic system, thermodynamic potentials are expected to be extensive, i.e., in this context, $G$ is expected to be a homogeneous function of degree one of its extensive argument $N$. Formally,
$$
G(T,P,alpha N) = alpha G(T,P,N)
$$
should hold for all positive values of $alpha$.
Thus, its is enough to take $alpha=1/N$ (allowed since $N>0$) to get
$$
G(T,P,1) = fracG(T,P,N)N
$$
i.e. $ G(T,P,N) = N G(T,P,1) $, where $ G(T,P,1) $ has no dependence on N.
On the other hand, $mu = left.fracpartialGpartialNright|_T,P$, and we arrive to the conclusion, since: $mu=G(T,P,1)$ is clearly independent on $N$.
This derivation makes clear that a key ingredient to get the result is the extensiveness of the Gibbs free energy, which is granted for large (macroscopic) thermodynamic systems, but could fail for finite systems made by a small number of particles.
Oh, that's so exactly what I needed. I'll keep the other answer as the "accepted one" (as it answered my edited question) - but many, many thanks for the insights you provided, and +1 of course!
– Sha Vuklia
Dec 11 at 17:56
add a comment |
The question contains a very common confusion about which independent variables a thermodynamic potential depends on.
$G$ is not a function of $S,T,V,P$. Actually the natural independent variables $G$ depends on can be obtained just looking at the differential: they are $T,P,N$. Each coefficient of the differential form $dG$ should be intended as a function of $T,P,N$, for a fluid one-component system.
Therefore, one would expect to have $mu=mu(P,T,N)$. However, for a normal thermodynamic system, thermodynamic potentials are expected to be extensive, i.e., in this context, $G$ is expected to be a homogeneous function of degree one of its extensive argument $N$. Formally,
$$
G(T,P,alpha N) = alpha G(T,P,N)
$$
should hold for all positive values of $alpha$.
Thus, its is enough to take $alpha=1/N$ (allowed since $N>0$) to get
$$
G(T,P,1) = fracG(T,P,N)N
$$
i.e. $ G(T,P,N) = N G(T,P,1) $, where $ G(T,P,1) $ has no dependence on N.
On the other hand, $mu = left.fracpartialGpartialNright|_T,P$, and we arrive to the conclusion, since: $mu=G(T,P,1)$ is clearly independent on $N$.
This derivation makes clear that a key ingredient to get the result is the extensiveness of the Gibbs free energy, which is granted for large (macroscopic) thermodynamic systems, but could fail for finite systems made by a small number of particles.
Oh, that's so exactly what I needed. I'll keep the other answer as the "accepted one" (as it answered my edited question) - but many, many thanks for the insights you provided, and +1 of course!
– Sha Vuklia
Dec 11 at 17:56
add a comment |
The question contains a very common confusion about which independent variables a thermodynamic potential depends on.
$G$ is not a function of $S,T,V,P$. Actually the natural independent variables $G$ depends on can be obtained just looking at the differential: they are $T,P,N$. Each coefficient of the differential form $dG$ should be intended as a function of $T,P,N$, for a fluid one-component system.
Therefore, one would expect to have $mu=mu(P,T,N)$. However, for a normal thermodynamic system, thermodynamic potentials are expected to be extensive, i.e., in this context, $G$ is expected to be a homogeneous function of degree one of its extensive argument $N$. Formally,
$$
G(T,P,alpha N) = alpha G(T,P,N)
$$
should hold for all positive values of $alpha$.
Thus, its is enough to take $alpha=1/N$ (allowed since $N>0$) to get
$$
G(T,P,1) = fracG(T,P,N)N
$$
i.e. $ G(T,P,N) = N G(T,P,1) $, where $ G(T,P,1) $ has no dependence on N.
On the other hand, $mu = left.fracpartialGpartialNright|_T,P$, and we arrive to the conclusion, since: $mu=G(T,P,1)$ is clearly independent on $N$.
This derivation makes clear that a key ingredient to get the result is the extensiveness of the Gibbs free energy, which is granted for large (macroscopic) thermodynamic systems, but could fail for finite systems made by a small number of particles.
The question contains a very common confusion about which independent variables a thermodynamic potential depends on.
$G$ is not a function of $S,T,V,P$. Actually the natural independent variables $G$ depends on can be obtained just looking at the differential: they are $T,P,N$. Each coefficient of the differential form $dG$ should be intended as a function of $T,P,N$, for a fluid one-component system.
Therefore, one would expect to have $mu=mu(P,T,N)$. However, for a normal thermodynamic system, thermodynamic potentials are expected to be extensive, i.e., in this context, $G$ is expected to be a homogeneous function of degree one of its extensive argument $N$. Formally,
$$
G(T,P,alpha N) = alpha G(T,P,N)
$$
should hold for all positive values of $alpha$.
Thus, its is enough to take $alpha=1/N$ (allowed since $N>0$) to get
$$
G(T,P,1) = fracG(T,P,N)N
$$
i.e. $ G(T,P,N) = N G(T,P,1) $, where $ G(T,P,1) $ has no dependence on N.
On the other hand, $mu = left.fracpartialGpartialNright|_T,P$, and we arrive to the conclusion, since: $mu=G(T,P,1)$ is clearly independent on $N$.
This derivation makes clear that a key ingredient to get the result is the extensiveness of the Gibbs free energy, which is granted for large (macroscopic) thermodynamic systems, but could fail for finite systems made by a small number of particles.
answered Dec 11 at 14:37
GiorgioP
1,369212
1,369212
Oh, that's so exactly what I needed. I'll keep the other answer as the "accepted one" (as it answered my edited question) - but many, many thanks for the insights you provided, and +1 of course!
– Sha Vuklia
Dec 11 at 17:56
add a comment |
Oh, that's so exactly what I needed. I'll keep the other answer as the "accepted one" (as it answered my edited question) - but many, many thanks for the insights you provided, and +1 of course!
– Sha Vuklia
Dec 11 at 17:56
Oh, that's so exactly what I needed. I'll keep the other answer as the "accepted one" (as it answered my edited question) - but many, many thanks for the insights you provided, and +1 of course!
– Sha Vuklia
Dec 11 at 17:56
Oh, that's so exactly what I needed. I'll keep the other answer as the "accepted one" (as it answered my edited question) - but many, many thanks for the insights you provided, and +1 of course!
– Sha Vuklia
Dec 11 at 17:56
add a comment |
Thanks for contributing an answer to Physics Stack Exchange!
- Please be sure to answer the question. Provide details and share your research!
But avoid …
- Asking for help, clarification, or responding to other answers.
- Making statements based on opinion; back them up with references or personal experience.
Use MathJax to format equations. MathJax reference.
To learn more, see our tips on writing great answers.
Some of your past answers have not been well-received, and you're in danger of being blocked from answering.
Please pay close attention to the following guidance:
- Please be sure to answer the question. Provide details and share your research!
But avoid …
- Asking for help, clarification, or responding to other answers.
- Making statements based on opinion; back them up with references or personal experience.
To learn more, see our tips on writing great answers.
Sign up or log in
StackExchange.ready(function ()
StackExchange.helpers.onClickDraftSave('#login-link');
);
Sign up using Google
Sign up using Facebook
Sign up using Email and Password
Post as a guest
Required, but never shown
StackExchange.ready(
function ()
StackExchange.openid.initPostLogin('.new-post-login', 'https%3a%2f%2fphysics.stackexchange.com%2fquestions%2f446602%2fproportionality-between-gibbs-free-energy-and-number-of-particles%23new-answer', 'question_page');
);
Post as a guest
Required, but never shown
Sign up or log in
StackExchange.ready(function ()
StackExchange.helpers.onClickDraftSave('#login-link');
);
Sign up using Google
Sign up using Facebook
Sign up using Email and Password
Post as a guest
Required, but never shown
Sign up or log in
StackExchange.ready(function ()
StackExchange.helpers.onClickDraftSave('#login-link');
);
Sign up using Google
Sign up using Facebook
Sign up using Email and Password
Post as a guest
Required, but never shown
Sign up or log in
StackExchange.ready(function ()
StackExchange.helpers.onClickDraftSave('#login-link');
);
Sign up using Google
Sign up using Facebook
Sign up using Email and Password
Sign up using Google
Sign up using Facebook
Sign up using Email and Password
Post as a guest
Required, but never shown
Required, but never shown
Required, but never shown
Required, but never shown
Required, but never shown
Required, but never shown
Required, but never shown
Required, but never shown
Required, but never shown
How can your substance have free energy if there are no molecules present? (N=0)
– Chester Miller
Dec 11 at 12:58
@ChesterMiller That's also a fair point.
– Sha Vuklia
Dec 11 at 12:58