Description Usage Arguments Details Value Algorithms References See Also Examples
Calculate equilibrium chemical activities of species from the affinities of formation of the species at unit activity.
1 2 3 4 5  equilibrate(aout, balance=NULL, loga.balance=NULL,
ispecies=1:length(aout$values), normalize=FALSE, as.residue=FALSE,
method=c("boltzmann", "reaction"), tol=.Machine$double.eps^0.25)
equil.boltzmann(Astar, n.balance, loga.balance)
equil.reaction(Astar, n.balance, loga.balance, tol=.Machine$double.eps^0.25)

aout 
list, output from 
balance 
character or numeric, how to balance the transformations 
ispecies 
numeric, which species to include 
normalize 
logical, normalize the molar formulas of species by the balancing coefficients? 
as.residue 
logical, report results for the normalized formulas? 
Astar 
numeric, affinities of formation reactions excluding species contribution 
n.balance 
numeric, number of moles of balancing component in the formation reactions of the species of interest 
loga.balance 
numeric (single value or vector), logarithm of total activity of balanced quantity 
method 
character, equilibration method to use 
tol 
numeric, convergence tolerance for 
equilibrate
calculates the chemical activities of species in metastable equilibrium, for constant temperature, pressure and chemical activities of basis species, using specified balancing constraints on reactions between species.
It takes as input aout
, the output from affinity
, which may be calculated from a multidimensional grid of conditions.
The equilibrium chemical activities of species are calculated using either the equil.reaction
or equil.boltzmann
functions, the latter only if the balance is on one mole of species.
aout
contains the chemical affinities of formation reactions of each species of interest.
equilibrate
needs to be provided constraints on how to balance the reactions representing transformations between the species.
balance
indicates the balancing component, according to the following scheme:
NULL: autoselect
name of basis species: balance on this basis species
length: balance on length of proteins
1: balance on one mole of species
numeric vector: userdefined constraints
The default value of NULL for balance
indicates to use the coefficients on the basis species that is present (i.e. with nonzero coefficients) in all formation reactions, or if that fails, to set the balance to 1.
However, if all the species (as listed in code aout$species
) are proteins (have an underscore character in their names), the default value of NULL for balance
indicates to use length as the balance.
NOTE: The summation of activities assumes an ideal system, so ‘molality’ is equivalent to ‘activity’ here.
loga.balance
gives the logarithm of the total activity of balance
(which is total activity of species for 1 or total activity of amino acid residueequivalents for length).
If loga.balance
is missing, its value is taken from the activities of species listed in aout
; this default is usually the desired operation.
The supplied value of loga.balance
may also be a vector of values, with length corresponding to the number of conditions in the calculations of affinity
.
normalize
if TRUE indicates to normalize the molar formulas of species by the balance coefficients.
This operation is intended for systems of proteins, whose conventional formulas are much larger than the basis speices.
The normalization also applies to the balancing coefficients, which as a result consist of 1s.
After normalization and equilibration, the equilibrium activities are then rescaled (for the original formulas of the species), unless as.residue
is TRUE.
equil.boltzmann
is used to calculate the equilibrium activities if balance
is 1 (or when normalize
or as.residue
is TRUE), otherwise equil.reaction
is called.
The default behavior can be overriden by specifying either boltzmann or reaction in method
.
Using equil.reaction
may be needed for systems with huge (negative or positive) affinities, where equil.boltzmann
produces a NaN result.
ispecies
can be supplied to identify a subset of the species to include in the calculation.
equil.reaction
and equil.boltzmann
each return a list with dimensions and length equal to those of Astar
, giving the log10
of the equilibrium activities of the species of interest.
equilibrate
returns a list, containing first the values in aout
, to which are appended m.balance
(the balancing coefficients if normalize
is TRUE, a vector of 1s otherwise), n.balance
(the balancing coefficients if normalize
is FALSE, a vector of 1s otherwise), loga.balance
, Astar
, and loga.equil
(the calculated equilibrium activities of the species).
The input values to equil.reaction
and equil.boltzmann
are in a list, Astar
, all elements of the list having the same dimensions; they can be vectors, matrices, or higherdimensionsal arrays.
Each list element contains the chemical affinities of the formation reactions of one of the species of interest (in dimensionless base10 units, i.e. A/2.303RT), calculated at unit activity of the species of interest.
The equilibrium base10 logarithm activities of the species of interest returned by either function satisfy the constraints that 1) the final chemical affinities of the formation reactions of the species are all equal and 2) the total activity of the balancing component is equal to (loga.balance
).
The first constraint does not impose a complete equilibrium, where the affinities of the formation reactions are all equal to zero, but allows for a metastable equilibrium, where the affinities of the formation reactions are equal to each other.
In equil.reaction
(the algorithm described in Dick, 2008 and the only one available prior to CHNOSZ_0.8), the calculations of relative abundances of species are based on a solving a system of equations representing the two constraints stated above.
The solution is found using uniroot
with a flexible method for generating initial guesses.
In equil.boltzmann
, the chemical activities of species are calculated using the Boltzmann distribution.
This calculation is faster than the algorithm of equil.reaction
, but is limited to systems where the transformations are all balanced on one mole of species.
If equil.boltzmann
is called with balance
other than 1, it stops with an error.
Dick, J. M. (2008) Calculation of the relative metastabilities of proteins using the CHNOSZ software package. Geochem. Trans. 9:10. https://doi.org/10.1186/14674866910
diagram
has examples of using equilibrate
to make equilibrium activity diagrams. revisit
can be used to perform further analysis of the equilibrium activities.
palply
is used by both equil.reaction
and equil.boltzmann
to parallelize intensive parts of the calculations.
1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23  ## equilibrium in a simple system:
## ionization of carbonic acid
basis("CHNOS+")
species(c("CO2", "HCO3", "CO32"))
# set unit activity of the species (0 = log10(1))
species(1:3, 0)
# calculate Astar (for unit activity)
res < 100
Astar < affinity(pH=c(0, 14, res))$values
# the logarithms of activity for a total activity
# of the balancing component (CO2) equal to 0.001
loga.boltz < equil.boltzmann(Astar, c(1, 1, 1), 0.001)
# calculated another way
loga.react < equil.reaction(Astar, c(1, 1, 1), rep(0.001, 100))
# probably close enough for most purposes
stopifnot(all.equal(loga.boltz, loga.react))
# the first ionization constant (pKa)
ipKa < which.min(abs(loga.boltz[[1]]  loga.boltz[[2]]))
pKa.equil < seq(0, 14, length.out=res)[ipKa]
# calculate logK directly
logK < subcrt(c("CO2","H2O","HCO3","H+"), c(1, 1, 1, 1), T=25)$out$logK
# we could decrease tolerance here by increasing res
stopifnot(all.equal(pKa.equil, logK, tolerance=1e2))

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