Why proton concentration is divided by 10⁻⁷?Unit of the equilibrium constant: contradiction of Bridgman's...
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Why proton concentration is divided by 10⁻⁷?
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$begingroup$
I am reviewing the book Biochemistry Concepts and Connections by Appling, Cahill, and Mathews and I cannot understand why they divide by the hydrogen concentration by $10^{-7}$. Why not just leave it at the antilog(-8.1) over $pu{1 M}$ like the other concentrations? I literally have see nothing else on the internet like this.
physical-chemistry equilibrium ph concentration free-energy
New contributor
$endgroup$
add a comment |
$begingroup$
I am reviewing the book Biochemistry Concepts and Connections by Appling, Cahill, and Mathews and I cannot understand why they divide by the hydrogen concentration by $10^{-7}$. Why not just leave it at the antilog(-8.1) over $pu{1 M}$ like the other concentrations? I literally have see nothing else on the internet like this.
physical-chemistry equilibrium ph concentration free-energy
New contributor
$endgroup$
add a comment |
$begingroup$
I am reviewing the book Biochemistry Concepts and Connections by Appling, Cahill, and Mathews and I cannot understand why they divide by the hydrogen concentration by $10^{-7}$. Why not just leave it at the antilog(-8.1) over $pu{1 M}$ like the other concentrations? I literally have see nothing else on the internet like this.
physical-chemistry equilibrium ph concentration free-energy
New contributor
$endgroup$
I am reviewing the book Biochemistry Concepts and Connections by Appling, Cahill, and Mathews and I cannot understand why they divide by the hydrogen concentration by $10^{-7}$. Why not just leave it at the antilog(-8.1) over $pu{1 M}$ like the other concentrations? I literally have see nothing else on the internet like this.
physical-chemistry equilibrium ph concentration free-energy
physical-chemistry equilibrium ph concentration free-energy
New contributor
New contributor
edited 18 hours ago
andselisk
17.4k656117
17.4k656117
New contributor
asked 18 hours ago
user75312user75312
412
412
New contributor
New contributor
add a comment |
add a comment |
2 Answers
2
active
oldest
votes
$begingroup$
The textbook is precisely correct.
The equilibrium constant $K$ which the logarithm is taken of is dimensionless, and includes activities or fugacities, and not concentrations and pressures.
In practice this is achieved by using standard states which refer to the pure materials: standard concentration $c^⦵$ and standard pressure $p^⦵$.
One must be very fastidious with units when finding the equilibrium constant.
For example, the reaction
$$ce{aA + bB <=> cC + dD}$$
equilibrium constant $K_c$ is exactly
$$K_c = frac{([ce{C}]/c^⦵)^ccdot ([ce{D}]/c^⦵)^d}{([ce{A}]/c^⦵)^acdot ([ce{B}]/c^⦵)^b}$$
For pure water in its standard state $c^⦵ = [ce{H+}] = pu{1e-7 M}$.
It also correlates with so-called biological standard state of $mathrm{pH} = 7$.
You probably haven't seen it before because many authors use sloppy notations omitting mentioning standard states since they can often be cancelled out.
In this case those cannot be cancelled out, and must be written explicitly.
In fact, your own textbook contains extensive explanation [1, p. 91]:
For chemical reactions the standard state for solutes is defined as $pu{1 M}$; however, in living cells the concentration of $[ce{H+}]$ is roughly $10^{-7}~mathrm M$, much lower than the standard value of $pu{1 M}$.
It is therefore appropriate to define the reference concentration of $ce{H+}$ in biochemical reactions relative to the $ce{H+}$ concentration found in the living state (i.e., $10^{-7}~mathrm M$), rather than the value $pu{1 M}$ defined by the chemical standard state.
Recall that when a solute in a dilute solution has a concentration of $pu{1 M}$, the activity of that solute is unity.
For the biochemical standard state we define the activity of $ce{H+}$ to be unity when $[ce{H+}] = 10^{-7}~mathrm M$.
[...]
- The mass action expression $Q$ is unitless.
We strip the units from each concentration term in $Q$ by dividing each by its
proper standard concentration (e.g., $pu{1 M}$ for all solutes
except $ce{H+}$; $10^{-7}~mathrm M$ for $ce{H+}$; $pu{1 bar}$ for gases, etc.).
Refrences
- Appling, D. R.; Anthony-Cahill, S. J.; Mathews, C. K. Biochemistry: Concepts and Connections (Global Edition); Pearson: Boston, 2015. ISBN 978-1-292-11210-7.
$endgroup$
3
$begingroup$
There are two standard states for [H+]. In the absence of a prime after the $^circ$, it is 1 M, and with the prime (biochemical standard state), it is $10^{-7}$ M.
$endgroup$
– Karsten Theis
11 hours ago
$begingroup$
Thanks, I have the second edition and this explanation is not on this page 91. Is it from Chapter 3? If so I will find it.
$endgroup$
– user75312
3 hours ago
$begingroup$
Nevermind, it is on page 59 of the second edition for those with the second edition.
$endgroup$
– user75312
3 hours ago
add a comment |
$begingroup$
For an explanation you may want to inspect Recommendations for Biochemical Equilibrium Data 1, which states:
Buffer and pH. If only a limited number of measurements are to be
made, they should be carried out at pH = 7.0 and, if possible, also
at a pH value at which the apparent equilibrium constant $K_c^prime$, has
little or no dependence on pH. ($K_c^prime$ is defined in a later
section.) If direct measurements at pH = 7.0 are not practicable, the
calculated values for this pH should be reported. The procedure used
in making these calculations must be carefully described. Care should
be taken that the solution is adequately buffered so that the pH is
well defined throughout the experiment. It is desirable to determine
the effect of varying the nature and concentration of the buffer in
order to identify buffer effects. Buffers that are known to interact
with reactants (including macromolecules) or salts, such as phosphate
or pyrophosphate in the presence of divalent metal ions, should be
avoided.
The highlighted portion means that reported values for biochemical reactions are (or should be) referenced to pH 7.0. The data in Table 3.6 refer to this biochemical standard state.
Another question on the subject of equilibrium constants also addresses the importance of properly considering reference states.
Reference
1 The Journal of Biological Chemistry (1976), Vol. 261, No. 22, pp. 6859-6885.
$endgroup$
add a comment |
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2 Answers
2
active
oldest
votes
2 Answers
2
active
oldest
votes
active
oldest
votes
active
oldest
votes
$begingroup$
The textbook is precisely correct.
The equilibrium constant $K$ which the logarithm is taken of is dimensionless, and includes activities or fugacities, and not concentrations and pressures.
In practice this is achieved by using standard states which refer to the pure materials: standard concentration $c^⦵$ and standard pressure $p^⦵$.
One must be very fastidious with units when finding the equilibrium constant.
For example, the reaction
$$ce{aA + bB <=> cC + dD}$$
equilibrium constant $K_c$ is exactly
$$K_c = frac{([ce{C}]/c^⦵)^ccdot ([ce{D}]/c^⦵)^d}{([ce{A}]/c^⦵)^acdot ([ce{B}]/c^⦵)^b}$$
For pure water in its standard state $c^⦵ = [ce{H+}] = pu{1e-7 M}$.
It also correlates with so-called biological standard state of $mathrm{pH} = 7$.
You probably haven't seen it before because many authors use sloppy notations omitting mentioning standard states since they can often be cancelled out.
In this case those cannot be cancelled out, and must be written explicitly.
In fact, your own textbook contains extensive explanation [1, p. 91]:
For chemical reactions the standard state for solutes is defined as $pu{1 M}$; however, in living cells the concentration of $[ce{H+}]$ is roughly $10^{-7}~mathrm M$, much lower than the standard value of $pu{1 M}$.
It is therefore appropriate to define the reference concentration of $ce{H+}$ in biochemical reactions relative to the $ce{H+}$ concentration found in the living state (i.e., $10^{-7}~mathrm M$), rather than the value $pu{1 M}$ defined by the chemical standard state.
Recall that when a solute in a dilute solution has a concentration of $pu{1 M}$, the activity of that solute is unity.
For the biochemical standard state we define the activity of $ce{H+}$ to be unity when $[ce{H+}] = 10^{-7}~mathrm M$.
[...]
- The mass action expression $Q$ is unitless.
We strip the units from each concentration term in $Q$ by dividing each by its
proper standard concentration (e.g., $pu{1 M}$ for all solutes
except $ce{H+}$; $10^{-7}~mathrm M$ for $ce{H+}$; $pu{1 bar}$ for gases, etc.).
Refrences
- Appling, D. R.; Anthony-Cahill, S. J.; Mathews, C. K. Biochemistry: Concepts and Connections (Global Edition); Pearson: Boston, 2015. ISBN 978-1-292-11210-7.
$endgroup$
3
$begingroup$
There are two standard states for [H+]. In the absence of a prime after the $^circ$, it is 1 M, and with the prime (biochemical standard state), it is $10^{-7}$ M.
$endgroup$
– Karsten Theis
11 hours ago
$begingroup$
Thanks, I have the second edition and this explanation is not on this page 91. Is it from Chapter 3? If so I will find it.
$endgroup$
– user75312
3 hours ago
$begingroup$
Nevermind, it is on page 59 of the second edition for those with the second edition.
$endgroup$
– user75312
3 hours ago
add a comment |
$begingroup$
The textbook is precisely correct.
The equilibrium constant $K$ which the logarithm is taken of is dimensionless, and includes activities or fugacities, and not concentrations and pressures.
In practice this is achieved by using standard states which refer to the pure materials: standard concentration $c^⦵$ and standard pressure $p^⦵$.
One must be very fastidious with units when finding the equilibrium constant.
For example, the reaction
$$ce{aA + bB <=> cC + dD}$$
equilibrium constant $K_c$ is exactly
$$K_c = frac{([ce{C}]/c^⦵)^ccdot ([ce{D}]/c^⦵)^d}{([ce{A}]/c^⦵)^acdot ([ce{B}]/c^⦵)^b}$$
For pure water in its standard state $c^⦵ = [ce{H+}] = pu{1e-7 M}$.
It also correlates with so-called biological standard state of $mathrm{pH} = 7$.
You probably haven't seen it before because many authors use sloppy notations omitting mentioning standard states since they can often be cancelled out.
In this case those cannot be cancelled out, and must be written explicitly.
In fact, your own textbook contains extensive explanation [1, p. 91]:
For chemical reactions the standard state for solutes is defined as $pu{1 M}$; however, in living cells the concentration of $[ce{H+}]$ is roughly $10^{-7}~mathrm M$, much lower than the standard value of $pu{1 M}$.
It is therefore appropriate to define the reference concentration of $ce{H+}$ in biochemical reactions relative to the $ce{H+}$ concentration found in the living state (i.e., $10^{-7}~mathrm M$), rather than the value $pu{1 M}$ defined by the chemical standard state.
Recall that when a solute in a dilute solution has a concentration of $pu{1 M}$, the activity of that solute is unity.
For the biochemical standard state we define the activity of $ce{H+}$ to be unity when $[ce{H+}] = 10^{-7}~mathrm M$.
[...]
- The mass action expression $Q$ is unitless.
We strip the units from each concentration term in $Q$ by dividing each by its
proper standard concentration (e.g., $pu{1 M}$ for all solutes
except $ce{H+}$; $10^{-7}~mathrm M$ for $ce{H+}$; $pu{1 bar}$ for gases, etc.).
Refrences
- Appling, D. R.; Anthony-Cahill, S. J.; Mathews, C. K. Biochemistry: Concepts and Connections (Global Edition); Pearson: Boston, 2015. ISBN 978-1-292-11210-7.
$endgroup$
3
$begingroup$
There are two standard states for [H+]. In the absence of a prime after the $^circ$, it is 1 M, and with the prime (biochemical standard state), it is $10^{-7}$ M.
$endgroup$
– Karsten Theis
11 hours ago
$begingroup$
Thanks, I have the second edition and this explanation is not on this page 91. Is it from Chapter 3? If so I will find it.
$endgroup$
– user75312
3 hours ago
$begingroup$
Nevermind, it is on page 59 of the second edition for those with the second edition.
$endgroup$
– user75312
3 hours ago
add a comment |
$begingroup$
The textbook is precisely correct.
The equilibrium constant $K$ which the logarithm is taken of is dimensionless, and includes activities or fugacities, and not concentrations and pressures.
In practice this is achieved by using standard states which refer to the pure materials: standard concentration $c^⦵$ and standard pressure $p^⦵$.
One must be very fastidious with units when finding the equilibrium constant.
For example, the reaction
$$ce{aA + bB <=> cC + dD}$$
equilibrium constant $K_c$ is exactly
$$K_c = frac{([ce{C}]/c^⦵)^ccdot ([ce{D}]/c^⦵)^d}{([ce{A}]/c^⦵)^acdot ([ce{B}]/c^⦵)^b}$$
For pure water in its standard state $c^⦵ = [ce{H+}] = pu{1e-7 M}$.
It also correlates with so-called biological standard state of $mathrm{pH} = 7$.
You probably haven't seen it before because many authors use sloppy notations omitting mentioning standard states since they can often be cancelled out.
In this case those cannot be cancelled out, and must be written explicitly.
In fact, your own textbook contains extensive explanation [1, p. 91]:
For chemical reactions the standard state for solutes is defined as $pu{1 M}$; however, in living cells the concentration of $[ce{H+}]$ is roughly $10^{-7}~mathrm M$, much lower than the standard value of $pu{1 M}$.
It is therefore appropriate to define the reference concentration of $ce{H+}$ in biochemical reactions relative to the $ce{H+}$ concentration found in the living state (i.e., $10^{-7}~mathrm M$), rather than the value $pu{1 M}$ defined by the chemical standard state.
Recall that when a solute in a dilute solution has a concentration of $pu{1 M}$, the activity of that solute is unity.
For the biochemical standard state we define the activity of $ce{H+}$ to be unity when $[ce{H+}] = 10^{-7}~mathrm M$.
[...]
- The mass action expression $Q$ is unitless.
We strip the units from each concentration term in $Q$ by dividing each by its
proper standard concentration (e.g., $pu{1 M}$ for all solutes
except $ce{H+}$; $10^{-7}~mathrm M$ for $ce{H+}$; $pu{1 bar}$ for gases, etc.).
Refrences
- Appling, D. R.; Anthony-Cahill, S. J.; Mathews, C. K. Biochemistry: Concepts and Connections (Global Edition); Pearson: Boston, 2015. ISBN 978-1-292-11210-7.
$endgroup$
The textbook is precisely correct.
The equilibrium constant $K$ which the logarithm is taken of is dimensionless, and includes activities or fugacities, and not concentrations and pressures.
In practice this is achieved by using standard states which refer to the pure materials: standard concentration $c^⦵$ and standard pressure $p^⦵$.
One must be very fastidious with units when finding the equilibrium constant.
For example, the reaction
$$ce{aA + bB <=> cC + dD}$$
equilibrium constant $K_c$ is exactly
$$K_c = frac{([ce{C}]/c^⦵)^ccdot ([ce{D}]/c^⦵)^d}{([ce{A}]/c^⦵)^acdot ([ce{B}]/c^⦵)^b}$$
For pure water in its standard state $c^⦵ = [ce{H+}] = pu{1e-7 M}$.
It also correlates with so-called biological standard state of $mathrm{pH} = 7$.
You probably haven't seen it before because many authors use sloppy notations omitting mentioning standard states since they can often be cancelled out.
In this case those cannot be cancelled out, and must be written explicitly.
In fact, your own textbook contains extensive explanation [1, p. 91]:
For chemical reactions the standard state for solutes is defined as $pu{1 M}$; however, in living cells the concentration of $[ce{H+}]$ is roughly $10^{-7}~mathrm M$, much lower than the standard value of $pu{1 M}$.
It is therefore appropriate to define the reference concentration of $ce{H+}$ in biochemical reactions relative to the $ce{H+}$ concentration found in the living state (i.e., $10^{-7}~mathrm M$), rather than the value $pu{1 M}$ defined by the chemical standard state.
Recall that when a solute in a dilute solution has a concentration of $pu{1 M}$, the activity of that solute is unity.
For the biochemical standard state we define the activity of $ce{H+}$ to be unity when $[ce{H+}] = 10^{-7}~mathrm M$.
[...]
- The mass action expression $Q$ is unitless.
We strip the units from each concentration term in $Q$ by dividing each by its
proper standard concentration (e.g., $pu{1 M}$ for all solutes
except $ce{H+}$; $10^{-7}~mathrm M$ for $ce{H+}$; $pu{1 bar}$ for gases, etc.).
Refrences
- Appling, D. R.; Anthony-Cahill, S. J.; Mathews, C. K. Biochemistry: Concepts and Connections (Global Edition); Pearson: Boston, 2015. ISBN 978-1-292-11210-7.
edited 8 hours ago
answered 18 hours ago
andseliskandselisk
17.4k656117
17.4k656117
3
$begingroup$
There are two standard states for [H+]. In the absence of a prime after the $^circ$, it is 1 M, and with the prime (biochemical standard state), it is $10^{-7}$ M.
$endgroup$
– Karsten Theis
11 hours ago
$begingroup$
Thanks, I have the second edition and this explanation is not on this page 91. Is it from Chapter 3? If so I will find it.
$endgroup$
– user75312
3 hours ago
$begingroup$
Nevermind, it is on page 59 of the second edition for those with the second edition.
$endgroup$
– user75312
3 hours ago
add a comment |
3
$begingroup$
There are two standard states for [H+]. In the absence of a prime after the $^circ$, it is 1 M, and with the prime (biochemical standard state), it is $10^{-7}$ M.
$endgroup$
– Karsten Theis
11 hours ago
$begingroup$
Thanks, I have the second edition and this explanation is not on this page 91. Is it from Chapter 3? If so I will find it.
$endgroup$
– user75312
3 hours ago
$begingroup$
Nevermind, it is on page 59 of the second edition for those with the second edition.
$endgroup$
– user75312
3 hours ago
3
3
$begingroup$
There are two standard states for [H+]. In the absence of a prime after the $^circ$, it is 1 M, and with the prime (biochemical standard state), it is $10^{-7}$ M.
$endgroup$
– Karsten Theis
11 hours ago
$begingroup$
There are two standard states for [H+]. In the absence of a prime after the $^circ$, it is 1 M, and with the prime (biochemical standard state), it is $10^{-7}$ M.
$endgroup$
– Karsten Theis
11 hours ago
$begingroup$
Thanks, I have the second edition and this explanation is not on this page 91. Is it from Chapter 3? If so I will find it.
$endgroup$
– user75312
3 hours ago
$begingroup$
Thanks, I have the second edition and this explanation is not on this page 91. Is it from Chapter 3? If so I will find it.
$endgroup$
– user75312
3 hours ago
$begingroup$
Nevermind, it is on page 59 of the second edition for those with the second edition.
$endgroup$
– user75312
3 hours ago
$begingroup$
Nevermind, it is on page 59 of the second edition for those with the second edition.
$endgroup$
– user75312
3 hours ago
add a comment |
$begingroup$
For an explanation you may want to inspect Recommendations for Biochemical Equilibrium Data 1, which states:
Buffer and pH. If only a limited number of measurements are to be
made, they should be carried out at pH = 7.0 and, if possible, also
at a pH value at which the apparent equilibrium constant $K_c^prime$, has
little or no dependence on pH. ($K_c^prime$ is defined in a later
section.) If direct measurements at pH = 7.0 are not practicable, the
calculated values for this pH should be reported. The procedure used
in making these calculations must be carefully described. Care should
be taken that the solution is adequately buffered so that the pH is
well defined throughout the experiment. It is desirable to determine
the effect of varying the nature and concentration of the buffer in
order to identify buffer effects. Buffers that are known to interact
with reactants (including macromolecules) or salts, such as phosphate
or pyrophosphate in the presence of divalent metal ions, should be
avoided.
The highlighted portion means that reported values for biochemical reactions are (or should be) referenced to pH 7.0. The data in Table 3.6 refer to this biochemical standard state.
Another question on the subject of equilibrium constants also addresses the importance of properly considering reference states.
Reference
1 The Journal of Biological Chemistry (1976), Vol. 261, No. 22, pp. 6859-6885.
$endgroup$
add a comment |
$begingroup$
For an explanation you may want to inspect Recommendations for Biochemical Equilibrium Data 1, which states:
Buffer and pH. If only a limited number of measurements are to be
made, they should be carried out at pH = 7.0 and, if possible, also
at a pH value at which the apparent equilibrium constant $K_c^prime$, has
little or no dependence on pH. ($K_c^prime$ is defined in a later
section.) If direct measurements at pH = 7.0 are not practicable, the
calculated values for this pH should be reported. The procedure used
in making these calculations must be carefully described. Care should
be taken that the solution is adequately buffered so that the pH is
well defined throughout the experiment. It is desirable to determine
the effect of varying the nature and concentration of the buffer in
order to identify buffer effects. Buffers that are known to interact
with reactants (including macromolecules) or salts, such as phosphate
or pyrophosphate in the presence of divalent metal ions, should be
avoided.
The highlighted portion means that reported values for biochemical reactions are (or should be) referenced to pH 7.0. The data in Table 3.6 refer to this biochemical standard state.
Another question on the subject of equilibrium constants also addresses the importance of properly considering reference states.
Reference
1 The Journal of Biological Chemistry (1976), Vol. 261, No. 22, pp. 6859-6885.
$endgroup$
add a comment |
$begingroup$
For an explanation you may want to inspect Recommendations for Biochemical Equilibrium Data 1, which states:
Buffer and pH. If only a limited number of measurements are to be
made, they should be carried out at pH = 7.0 and, if possible, also
at a pH value at which the apparent equilibrium constant $K_c^prime$, has
little or no dependence on pH. ($K_c^prime$ is defined in a later
section.) If direct measurements at pH = 7.0 are not practicable, the
calculated values for this pH should be reported. The procedure used
in making these calculations must be carefully described. Care should
be taken that the solution is adequately buffered so that the pH is
well defined throughout the experiment. It is desirable to determine
the effect of varying the nature and concentration of the buffer in
order to identify buffer effects. Buffers that are known to interact
with reactants (including macromolecules) or salts, such as phosphate
or pyrophosphate in the presence of divalent metal ions, should be
avoided.
The highlighted portion means that reported values for biochemical reactions are (or should be) referenced to pH 7.0. The data in Table 3.6 refer to this biochemical standard state.
Another question on the subject of equilibrium constants also addresses the importance of properly considering reference states.
Reference
1 The Journal of Biological Chemistry (1976), Vol. 261, No. 22, pp. 6859-6885.
$endgroup$
For an explanation you may want to inspect Recommendations for Biochemical Equilibrium Data 1, which states:
Buffer and pH. If only a limited number of measurements are to be
made, they should be carried out at pH = 7.0 and, if possible, also
at a pH value at which the apparent equilibrium constant $K_c^prime$, has
little or no dependence on pH. ($K_c^prime$ is defined in a later
section.) If direct measurements at pH = 7.0 are not practicable, the
calculated values for this pH should be reported. The procedure used
in making these calculations must be carefully described. Care should
be taken that the solution is adequately buffered so that the pH is
well defined throughout the experiment. It is desirable to determine
the effect of varying the nature and concentration of the buffer in
order to identify buffer effects. Buffers that are known to interact
with reactants (including macromolecules) or salts, such as phosphate
or pyrophosphate in the presence of divalent metal ions, should be
avoided.
The highlighted portion means that reported values for biochemical reactions are (or should be) referenced to pH 7.0. The data in Table 3.6 refer to this biochemical standard state.
Another question on the subject of equilibrium constants also addresses the importance of properly considering reference states.
Reference
1 The Journal of Biological Chemistry (1976), Vol. 261, No. 22, pp. 6859-6885.
edited 11 hours ago
answered 14 hours ago
Night WriterNight Writer
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