Chem 301 log C pH - 1

Graphical Solutions for Sets of Simultaneous Equations - In the last chapter (3) we first saw log C pH diagrams these help visualize the speciation of acids and bases over a wide range of conditions we can use these diagrams to determine the pH and the speciation of the whole solution at equilibrium before computers were widely accessible, this was the only way to solve acid/base problems a log C-pH diagram contains information about the relevant acidity constants (indicated by the intersection points of conjugate acid/base pairs), the dissociation of water (indicated by the relative positions of the H+ and OH- lines), and the total amount of each weak acid/base group in the system (indicated by the largest value that log C approaches for the individual acid and base species) once the graph is drawn, we determine the equilibrium speciation of the system by finding the unique pH where the charge balance is satisfied Log C pH Diagrams Using Excel spreadsheet eg 5 x 10-4 M HAc solution Ka = 1.8 x 10-5 log[HAc]

set up table with 6 columns: [H+] [A-] [HA] pH log[A-] will also need 2 cells to input the Ka and TOTA in my eg, B5 holds Ka (1.8 x 10-5) and C5 holds TOTA (5.00 x 10-4 M)

See Goodies list on my website it has this program there

Column A [H+] go from 10-14 up to 10-1

Ka [A ] = (TOTA) 1 = (TOTA) = (TOTA) K a + [H + ] Column B [A ]

-

1 [H+ ] 1+ Ka

= $C$5 * (1/(1+(A8/$B$5)))

Column C [HA]

[HA] = (TOTA) 0 = (TOTA)

[H+ ] = (TOTA) K a + [H +]

1 1+ Ka [H+ ]

= $C$5 * (1/(1+($B$5/A8))) then highlight columns D, E and F, choose XY scatter and plot the pH scale will typically always be 0 14, but the log C scale can vary from 0 -8 or 0 -10 How to Draw log C-pH Diagrams - these can be sketched out quite quickly on graph paper the y axis is usually log C but occasionally is pC, (-log C), resulting in positive numbers on the axis 1. Make square with log C on y axis start at 0 (at the top) -8 (at the bottom) pH is on the x axis 0 to 14 2. plot H+ line it will pass through 0,0 and 7,7 (and will have a slope of 1)

Chem 301 log C pH - 2

3. plot OH- line it will pass through14,0 and 7,7 (and will have a slope of +1) 4. plot weak acid/base MB line straight line at log C 5. plot HA line before pKa it will be horizontal at log C past pKa it will have slope of 1 (ie it will be parallel to the H+ line) and it will intercept the log C line at the pKa 6. plot A- line past pKa it will be horizontal at log C before pKa it will have slope of +1 (ie it will be parallel to the OH- line) and it will intercept the log C line at the pKa 7. plot the intersection of the HA and A- lines which will occur at 0.3 log C units below the MB line at the pKa when pH = pKa, [HA] = [A-] = 0.5TOTA log [HA] = log [A-] = log (0.5) + log (TOTA) = -0.3 + log (TOTA) i.e. both are 0.3 log units below the MB line 8. join the 2 parts of the HA and A- lines with a nice smooth curve eg 10-3 M HCN Solution pKa = 9.3

steps 1 3 are always the same 4. make a horizontal line at log C = -3 this is the MB line make a mark on this line at pH = 9.3 (the pKa) the HCN and CN- lines will intersect there 5. to draw the HCN line, line up the ruler at the mark on the MB line at 9.3 draw a line exactly parallel to the H+ line, going through the above mark 6. to draw the CN- line, draw a line parallel to the OH- line, going through the same mark 7. the intersection of the HCN and CN- lines occurs at pH = 9.3 and at log C = -3.3 Determining pH and concentration of all species from the pC-pH diagram: the diagram incorporates all the information required i.e. the Ka's and the MB's now we find the pH where the charge balance is satisfied i.e. we find the point on the diagram where the RHS of the CB = the LHS this is the only place that the diagram can be used to obtain equilibrium concentrations once we know the pH at which the CB is satisfied, simply determine the concentrations of all the species at this pH from the diagram eg What is the pH and the concentration of all species at equilibrium in a 10-3 M HCN solution? 1. spp: 2. K's: 3. MB's 4. CB: H+ Kw OHHCN CN-

Ka = 10-9.3

TOTCN = [HCN] + [CN-] = 10-3 M [H+] = [OH-] + [CN-]

Chem 301 log C pH - 3

now we find the pH where the charge balance is satisfied ie where the H+ line is equal to the sum of the OH- and CN- lines the sum of the lines will always be higher than or as high as the uppermost line at a given pH typically, one line is dominant over the other at most values of pH (the one that is higher) if this is the case in the region where the CB is satisfied, then the problem is easy to solve graphically we just follow the uppermost lines for each side of the CB and where they cross is where the CB is satisfied eg on the LHS we only have the H+ line so we follow the H+ line until it crosses the sum of the CN- and OH- lines now consider the RHS of the CB OH- does not contribute significantly to the CB at pH < 11 ie at pH < 11, CN- becomes the dominant species on the RHS so we follow the CN- line until it crosses the H+ line this occurs at point A on my diagram ie pH ~ 6.2 drop a line straight down at this pH and read off concentrations of all the species present at this pH, [H+] = 10-6.2 M = 6.3 x 10-7 M [OH-] = 10-7.8 M = 1.585 x 10-8 M -3 -6.2 [HCN] = 10 [CN ] 10 M Now, the last step is the check the charge balance: 10-6.2 = 10-7.8 + 10-6.2 ok

we can calculate the error in the CB by comparing the net charge to the total positive or negative charge if the CB is satisfied at a pH close to where the OH- and CN- lines cross, we need to add the two lines together at this point, [OH-] = [CN-] the sum of the two lines = log ([OH-] + [CN-]) ; NB log (A + B) log (A) + log (B) so the sum of the two lines = log (2[OH-]) = log 2 + log [OH-] since log 2 = 0.3, we can draw a smooth curve joining the CN- and OH- lines through a point 0.3 log units directly above the intersection note that using the graph as I have described is essentially the same thing as making simplifying assumptions and then solving the problem analytically ie assuming [H+] >> [OH-] the CB becomes [H+] = [CN-] and it is satisfied when the H+ line crosses the CN- line (which is exactly what I did) the nice thing about the graph is you can see if your assumptions are true by how high the H+ line is relative to the OH- line often, even if we need to solve a problem numerically (ie need more accuracy then the diagram provides), it is still useful to draw log C-pH diagrams, as they allow us to check any assumptions we might make to facilitate solving immediately however, more often an answer with 0.05 pH units is obtainable and satisfactory and so the graphical method is sufficient

Chem 301 log C pH - 4

to sum the lines of 2 terms on one side of the charge balance, we must take the antilog of both terms, add them together, and then take the log of the sum and plot the sum-line a general rule of thumb when summing lines is: if 2 lines are separated by < 1 log unit, we consider that their sum is somewhat larger than the value of the upper line alone but if the lower line is > 1 log unit lower, we can probably ignore it without affecting the results in summary, we can solve a problem analytically, or using spreadsheets, or with a log C-pH diagram only the graphical approach allows us to visualize the behaviour of species at different pH's this isn't so impressive with the simple examples that we've done so far, but becomes more so when we deal with more complex systems eg What is the pH and the concentration of all species at equilibrium in a 10-3 M NaCN solution? 1. spp: 2. K's: H+ Kw OHHCN CNNa+

Ka = 10-9.3 TOTNa = [Na+] = 10-3 M

3. MB's TOTCN = [HCN] + [CN-] = 10-3 M 4. CB: [H+] + [Na+] = [OH-] + [CN-]

our log C-pH diagram is exactly the same, except that there is one additional line for the MB of Na+ this is simply a horizontal line at log C = -3 now we find the pH where the charge balance is satisfied ie where the sum of the H+ and Na+ lines is equal to the sum of the OH- and CN- lines eg on the LHS we need to sum the 2 lines for H+ and Na+ but the only place on the diagram where H+ makes a significant contribution to the charge balance is at pH < 3 and in this region it doesn't come anywhere near the RHS lines (CN- and OH-) so once pH is > 3, [Na+] is so much higher than [H+] that we can ignore the [H+] this is indicated by how the H+ line dips way below the Na+ line the further apart the 2 lines are, the more dominant is the species whose line is on top ie the sum of the 2 lines just becomes the upper line in this case the Na+ line so we follow the Na+ line until it crosses the sum of the CN- and OH- lines now consider the RHS of the CB OH- does not contribute significantly to the CB at pH < 11 ie at pH < 11, CN- becomes the dominant species on the RHS so we follow the CN- line until it crosses sum of the LHS lines, in this case, the Na+ line but this occurs at a very flat point on the diagram, where both appear to be 10-3 M we cannot distinguish the exact point where the two lines cross there is one, we just can't see it on the scale of the diagram ultimately, this is because we have two very large terms in the CB (relative to the other two), [Na+] and [CN-]

Chem 301 log C pH - 5

this means that the CB is approximately satisfied over a very wide range of pH, where [Na+] ~ [CN must eliminate one of these large numbers from each side of the CB to get around this can combine the CB with the two MB's to get rid of the large terms we know that TOTNa = TOTCN i.e. [Na+] = [HCN] + [CN-] + sub into CB: [H ] + [HCN] + [CN-] = [OH-] + [CN-] or [H+] + [HCN] = [OH-]

this version of the CB will be a lot easier to solve at pH > 3, the HCN line dominates over the H+ line so follow the HCN line until it crosses the OH- line this occurs at pH = 10.1 drop a line straight down and read off concentrations of all the species present at this pH, [H+] = 10-10.1 M = 7.94 x 10-11 M [OH-] = 10-3.9 = 1.26 x 10-4 M + -3 -3.05 [Na ] = 10 M [CN ] 10 M = 8.91 x 10-4 M [HCN] = 10-3.9 = 1.26 x 10-4 M check CB: 7.94 x 10-11 + 1 x 10-3 = 1.26 x 10-4 + 8.91 x 10-4 ok

whenever the CB appears to be balanced over a wide pH range i.e. when you are in the flat region of the diagram, must combine the CB with the MB's to eliminate the largest number on each side of the CB Is there a way to write the improved CB directly? now we know how to draw pC-pH graphs and how to use them to solve problems i.e. see where the diagram satisfies the CB but we found that sometimes the CB has a very large term on each side this results in the CB being satisfied in a flat section of the curve we can't see the intersection points to get around this, subbed MB's into the CB to get rid of the big term to avoid having to do this, instead of using the CB to solve the problem, use the proton condition this is a mass balance on H which we've ignored so far the proton condition can be derived by combining the CB with one or more MB's ultimately, we can use the PC (aka TOTH) even when all charged species in a solution are not known i.e. when we would not be able to do the CB Proton Condition Mass Balance on H it would be nice to not have to convert the CB by incorporating MB's to use the graph to solve to do this we set baseline conditions other than zero for H ie for MB's so far eg TOTCO3 = [H2CO3] = [HCO3-] + [CO32-] = 10-3 M we are implicitly comparing it to a solution with zero M CO3 species if we don't have a good reason to define a non-zero baseline, we don't, and we don't even think about it but for H+ it is better to compare to a non-zero baseline

Chem 301 log C pH - 6

this is because the number of H atoms associated with H2O is huge ie 2 x 55.6 M this is humongous compared to the concentrations of virtually all the other species in solution it is difficult to map changes in H+ concentration in solution so instead, we keep track only of changes in concentration of other H-bearing species ie the proton condition species or solutions with protons > baseline = excess H species or solutions with protons < baseline = deficient H proton condition (PC) = mass balance on H using a non-zero baseline the proton condition contains the same information as the CB but the PC is a more convenient form to use with pC-pH graphs to be most useful the final equation must not contain terms for species that dominate at equilibrium we want the dominant species to be the reference species so we select one species from each type a or b group to be the reference species for that group also select all salts to be reference species for the acid/base groups in solution it is not always clear as to which species to pick as the reference we want to pick the species that will be dominant once the solution achieves equilibrium this is essentially the same thing as eliminating the large terms from the CB ie this eliminates overlapping regions of pH when balancing the LHS and RHS of the CB on the graph because different species are dominant in different systems, the best choices for reference species will vary from one system to another however, H2O is always dominant over H+ and OH- it is always the reference species for the type a species so we represent each species present at equilibrium as a combination of reference species and H+ ions eg 0.1 M H3PO4 solution if we select HPO42- as the reference species then H3PO4 has 2 excess protons H2PO4- has 1 excess proton PO43- has 1 deficiency in protons, or (1) excess protons collectively the reference species define the baseline for determining TOTH TOTH = net concentration of H ie the sum of excess H species the sum of deficient H species a solution made up entirely of baseline species is defined as having TOTH = 0 the PC is sometimes called the TOTH balance or TOTH equation

Chem 301 log C pH - 7

Writing the Proton Condition 1. Define the baseline concentration of H (ie select reference species) 2. Define H+ excess or deficient of all species in equilibrium solution get the TOTH equation 3. Calculate TOTHin i.e. H+ input (relative to baseline) total protons remains constant as initial species are converted to equilibrium species i.e. TOTHin = TOTHeq Proton Condition positive species = negative species excess protons deficient protons

eg 10-3 M Na2CO3 + 10-6 M HCN have 4 groups, require 4 reference species: H2O, one from the carbonate group, one from the cyanide group and Na+ let's arbitrarily choose HCN and HCO3- as the reference species for the cyanide and carbonate groups respectively set up an H table: H+ excess 0 +1 H2O H3O+ HCN HCO3H2CO3 Na+ H2O HCN

equib spp

-1 OHCNCO32-

Concentration (M)

initial spp Na2CO3

55.6 10-6 10-3

TOTHeq = (CH2OnH2O + CH+nH+ + COH-nOH-) + (CHCNnHCN + CCN-nCN-) + (CH2CO3nH2CO3 + CHCO3nHCO3 + CCO3nCO3) + (CNa+nNa+) = 0 + [H+](1) + [OH-](-1) + 0 + [CN-](-1) + [H2CO3](1) + 0 + [CO32-](-1) + 0 I've shown all species present at equilibrium, including the reference species, which ni = 0, so they do not contribute to the TOTH equation we don't normally bother to write the reference species TOTHin = (CH2OnH2O)+ (CHCNnHCN) + (CCO3nCO3) + (CNa+nNa+) TOTHin = 0 + 0 + (-1)(10-6) + 0 = -10-6 M as the solution achieves equilibrium , H+ may transfer from 1 species to another, but the total concentration of protons must remain constant i.e. TOTHin = TOTHeq

-10-6 M = [H+] - [OH-] - [CN-] + [H2CO3] - [CO32-] for the initial (input) species, must include all chemicals in solution prior to equilibrium

Chem 301 log C pH - 8

in this example we knew all the input but in other systems, we might know the complete composition of the solution at some initial point without knowing exactly what chemicals were added to prepare that solution and also know the amount of any chemicals added subsequently in these cases, consider the ultimate solution to be a combination of the initial and the additional chemicals PC vs TOTH Equation the difference is largely semantic, although they came out of different approaches to equilibrium problem solving PC species are defined as being proton excess or deficient relative to reference species because it was developed for use with log C-pH diagrams, it is always written so that each term is positive group like-signed terms together eg 0.1 M Na3PO4 solution Na+ and HPO42- are reference species set up an H table: -1 OHPO43Na3PO4 PC: 0.1 + [H+] + 2[H3PO4] + [H2PO4-] = [OH-] + [PO43-] H+ excess 0 H2O HPO42Na+ H2O +1 +2 H3PO4 55.6 0.1 Conc. (M)

Equib spp Initial spp

TOTH developed with the advent of computers and the use of equilibrium modelling software species are called components always written with the input species on one side and the equilibrium species on the other for the example above: -0.1 = [H+] + 2[H3PO4] + [H2PO4-] - [OH-] - [PO43-]

sometimes we do not know what was in the initial solution then you cannot write the CB in the text he goes through an example where we know the equilibrium pH and the speciation of the CO3 species however, we do not know what else is present in the solution there is no info on what cations are present for example and all the cations should be in the CB in this case we can derive a CB (the text does this), but it is very tedious it is much easier to do a PC or TOTH for these, you don't need to refer to unspecified cations and anions at all so while not being a CB in itself, the PC is a way to characterize the same information as in the CB, even if we don't know all the charged species in a solution

Chem 301 log C pH - 9

we can also use the PC to evaluate the dose of a chemical that is required to adjust a solution to a specified endpoint Choosing Reference Species the primary reason for developing the PC was to use it with log C-pH graphs to solve equilibrium problems especially in cases where we can't use the CB directly ie when we have to combine it with MB's to remove the large concentrations from each side in other words, we want to have an equation that does not contain any of the dominant species of an acid or base at equilibrium since the reference species are not present at equilibrium, we choose the dominant species to be the baseline species H2O is always dominant over H+ and OH- and is always a reference species type c species i.e. salt ions such as Na+ are almost always the dominant form at equilibrium, so we choose them as the reference species but for groups of weak acids and bases, it is not so obvious as to which one to pick let's begin with the correct assumption that solutions have no memory i.e. if the solution has certain concentrations of species at equilibrium, it doesn't matter what we started with ie how we made it up in fact, it is impossible to tell how it started out we can only say that all the species in the equilibrium system were added in some form we are free to imagine the solution was concocted in any way we like so let's imagine we make up a solution by adding everything to it except H+ then we add the H+ (this isn't realistic of course when we add anions, must also add cations) as we add the H+, it will combine first with the strongest base present in the system if there is still some left over, it will then combine with the second strongest base, then the third strongest etc, until all the H+ is consumed once the H+ is consumed, any weaker bases will not be converted back to their conjugate acids, and will remain in the base form we then examine each acid/base pair to determine which is the dominant species at equilibrium, and choose that as its baseline species this method almost always correctly identifies the dominant species in a system the only time it might fail is when there are several acid base pairs in the system with nearly identical Ka's but even in this case, when we try to evaluate the PC graphically, it will be evident which species should have been chose as the reference species we can then rewrite the PC and solve the problem eg 0.1 M NaH2PO4 solution

TOTHin = 2(0.1 M) = 0.2 M base/acid PO43-/HPO42HPO42-/H2PO4H2PO4-/H3PO4 pKa 12.35 7.20 2.16 TOTPO4 0.1 0.1 0 H+ available 0.2 0.1 0

Chem 301 log C pH - 10

so in this solution the dominant species (and hence what we would pick for our reference species) is H2PO4i.e. all the PO43- will be converted to HPO42 all the HPO42- will be converted to H2PO4 but this leaves no H+ left to form H3PO4 ie no H3PO4 is possible eg A solution is made up of the following: 5 x 10-3 M HAc 3.2 x 10-3 MNH3 1.2 x 10-3 M NaCN 5 x 10-4 M NaOH

a. Write the proton condition. Clearly show how you choose your reference (baseline) species. b. Write the H balance (TOTH equation) for this sample. pKa's at the back. 1. calculate the H+ available: Havail = 5 x 10-3

note: if you don't include OH- in the acid/base table, then: Havail = 5 x 10-3 + (-5 x 10-4) = 4.5 x 10-3 M 2. set up acid/base table base/acid OH-/H2O NH3/NH4+ CN-/HCN Ac-/HAc pKa 14.00 9.25 9.24 4.76 TOTA 0.5 x 10-3 3.2 x 10-3 1.2 x 10-3 5 x 10-3 H+ available 5 x 10-3 4.5 x 10-3 1.3 x 10-3 0.1 x 10-3

at equilibrium the dominant species will be: H2O, NH4+, HCN, Ac-, and Na+ 3. set up proton table: -1 OHNH3 CNH+ excess 0 H2O NH4+ +1 Conc. (M)

Equib spp

HCN
AcNa+ H2O 55.6 5 x 10-4 3.2 x 10-3 1.2 x 10-3 5 x 10-3

Initial spp

NaOH
NH3 NaCN

TOTHin = -[OH-] [NH3] [CN-] + [HAc] TOTHin = -5 x 10-4 3.2 x 10-3 1.2 x 10-3 + 5 x 10-3 = 0.1 x 10-3 M TOTHeq = [H+] + [HAc] [OH-] [NH3] [CN-] TOTHin = TOTHeq 0.1 x 10-3 = [H+] + [HAc] [OH-] [NH3] [CN-]

Chem 301 log C pH - 11

PC:

[H+] + [HAc] = [OH-] + [NH3] + [CN-] + 0.1 x 10-3

Use of Log C pH Diagrams and the PC with a little practice, this can be a much faster way of determining equilibrium speciation in a system compared to the numerical methods also, it is more intuitive it is also very useful for predicting how the speciation would change with pH, which the numerical methods do not provide any information on at all Non-obvious Proton Conditions the PC and TOTH are simply mathematical statements that protons are conserved like all other species in a system we define our reference species, set up a proton table and assign species to excess and deficient columns but in some cases, it is not obvious as to whether a species is excess or deficient consider the example for set-up that we did earlier Cd2+ formed a bunch of complex ions what is the proton level of each of the ions? eg 5 x 10-6 M CdCO3 10-3 M H3PO4 10-3 M NaCl

let's arbitrarily pick H2O, H2PO4-, HCO3-, Cd2+, Na+, and Cl- as baseline species now we set up a proton table where do the complex ions go? eg Cd ions that combine with hydroxide Cd2+ is a reference species ie it is proton neutral OH- is a proton deficient species combining a 1 proton-deficient species with a proton-neutral species results in a 1 proton deficient species ie Cd(OH)+ would go in the 1 column similarly, Cd(OH)2 goes in the 2 column etc Equib spp -4 -3 H+ excess -2 PO43Cd(OH)2 Cd(PO4)-1 OHCO32HPO42CdOH+ CdCO3 0 H2O HCO3H2PO4Cd2+ +1 H+ H2CO3 H3PO4 Conc

Cd(OH)4

2-

Cd(OH)3 Cd(CO3)34-

Na+ ClCdCl+ CdCl2 CdCl3Init spp CdCO3 H3PO4 NaCl TOTHin = (-1)(5 x 10-6) + (1)(10-3) = 9.995 x 10-3 M TOTHeq = [H+] + [H2CO3] + [H3PO4] [OH-] [CO32-] [HPO42-] 2[PO43-] [CdOH+] 2Cd(OH)2 3[Cd(OH)3-] 4[Cd(OH)42-] [CdCO3] 3[Cd(CO3)34-] - 2[CdPO4-] 5 x 10-6 10-3 10-3

Chem 301 log C pH - 12

species that must be included in the PC are not only those that can react with protons directly, but also any species that can combine with others that react with protons can also use this approach to determine the proton levels of species that enter or exit the aqueous phase via exchange with a gas or suspended solid