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Two ways to analyze a mixture. Figure 19-5 shows the spectrum of the indicator bromothymol blue adjusted to several pH values. The spectrum at pHis that of the pure blue form and the spectrum at pH 1.8is that of the pure yellow form. At other pHvalues, there is a mixture of the two forms. The total concentration isand the path length isin all spectra. For the purpose of calculation, assume that there are more than two significant digits in concentration and path length. Absorbance at the dots on three of the curves in Figure 19-5 is given in the table.

(a) Prepare a spreadsheet like Figure 19-3 to use absorption at all six wavelengths to find[In-]and[HIn]in the mixture. Comment on the sum[In-]+[HIn].

(b) From[In-]in the mixture, and frompKa=7.10for HIn,calculate theof the mixture. (This calculation is the source of pH labels in the figure.)

(c) Use Equations 19-6 at the peak wavelengths ofto findin the mixture. Compare your answers to those in (a). Which answers, (a) or (c), are probably more accurate? Why?

Short Answer

Expert verified

(a) The value of [In-]and[HIn]are role="math" localid="1667561090010" In-=3.28.10-6M,HIn=6.91.10-6M.

(b) Theof the mixture is pH=6.78.

(c) The value of role="math" localid="1667560565259" In-andHInare role="math" localid="1667560605859" In-=3.31.10-6M,HIn=6.97.10-6M. The answer (a) is probably more accurate.

Step by step solution

01

State Beer’s Law:

Beer's law states that through the sample and the concentration of the absorbing species, the absorbance is proportional to the path length.

A=蔚产颁

A is the absorbance, is the molar absorptivity,b is the length of light path, C is the concentration.

02

(a) Prepare a spreadsheet and find the values of In- and HIn using Beer’s Law:

Hence, the spreadsheet is,

Calculatevalues using Beer鈥檚 Law,

=Ab[standard]

Thus, Column can be calculated by using the formula,

A=xb[X]guess+yb[Y]Guess

Hence, in cell D10 and D11 we know the values.

Take the concentration is 0.001 M for each compound.

Thus, we calculated column G and H column.

Calculate the sum in column H8.

Use the solver to calculate the concentration of unknown and highlight the cell.

Select data tab Solver and enter H8 in Set Objective.

Select the min button and in by Changing Variables enter D10 and D11.

Thus, solving method should be GRG nonlinear.

Hence, set Constraint Precision to a small number such as 1E-12.

Click solve, the values appears in the cell D10 and D11.

Therefore, the values of[In-]and[HIn] are In-=3.28.10-6M,HIn=6.91.10-6M.

03

(b) Determine the pH value using Henderson-Hassel Balch equation:

Consider the Henderson-Hassel Balch equation,

pH=pKa+log[I-][HIn]

pH=7.10+log7.10+log3.2810-66.9110-6

pH = 6.78

04

(c) Find the concentration of [In-] and [HIn] and use the spreadsheet values:

Calculate the concentration ofIn- by using the formula,

[ln]=AmixtureoHInbAmixtureoHIn'blInb鈥呪赌呪赌呪赌HHInboInb鈥呪赌呪赌呪赌oHlnb

Use the values from the mention spreadsheet,

ln=0.265344000.27250076003440081100500ln=(0.265500)(344000.272)(7600500)(3440081100)ln=3.31106M

Find the concentration of HIn,

[Hln]=oInbAmixtureo^llnbAmixtureoInboHInbo^lnboHInb

Use the values from spreadsheet,

Hln]=76000.265811000.27276003440081100500

[Hln]=(76000.272)-(811000.265)(7600500)-(3440081100)[Hln]=6.9710-6M

Therefore, the answer (a) is probably more accurate.

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Most popular questions from this chapter

The figure shows spectra of1.0010-4MMnO4-,1.0010-4and an unknown mixture of both, all in1.000cmpath length cells. Absorbances are given in the table. Use the least squares procedure in Figure 19-3 to find the concentration of each species in the mixture.

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Here is an immunoassay to measure explosives such as trinitrotoluene (TNT) in organic solvent extracts of soil. The assay employs a flow cytometer, which counts small particles (such as living cells) flowing through a narrow tube past a detector. The cytometer in this experiment irradiates the particles with a green

laser and measures fluorescence from each particle as it flows past the detector.

1. Antibodies that bind TNT are chemically attached to 5mmdiameter latex beads.

2. The beads are incubated with a fluorescent derivative of TNT to saturate the antibodies, and excess TNT derivative is removed. The beads are resuspended in aqueous detergent.

3. 5mlof the suspension are added to 100mlof sample or standard. TNT in the sample or standard displaces some derivatized TNT from bound antibodies. The higher the concentration of TNT, the more derivatized TNT is displaced.

4. An aliquot is injected into the flow cytometer, which measures fluorescence of individual beads as they pass the detector. The figure shows median fluorescence intensity 6 standard deviation. TNT can be quantified in the ppb to ppm range.

Draw pictures showing the state of the beads in steps 1, 2, and 3and explain how this method works.

Chemical equilibrium and analysis of a mixture. (Warning! This is a long problem.) A remote optical sensor for CO2in the ocean was designed to operate without the need for calibration.33


The sensor compartment is separated from seawater by a silicone membrane through which CO2, but not dissolved ions, can diffuse. Inside the sensor, CO2equilibrates with HCO3and CO32. For each

measurement, the sensor is flushed with fresh solution containingbromothymol blue indicator. All indicator is in the formnear neutral pH, so we can

write two mass balances:

[HIn]+[ln2]=FIn=50.0渭惭补苍诲[Na+]=F狈伪=50.0渭惭+42.0渭惭=92.0渭惭

has an absorbance maximum at 434 nm andhas a maximum at 620 nm. The sensor measures the absorbance ratio RA=A620/A434reproducibly without need for calibration. From this ratio, we can findin the seawater as outlined here:

(a).From Beer鈥檚 law for the mixture, write equations forin terms of the absorbance at 620 and 434 nmThen show that

[ln2][Hln]=RA434HHn6,20Hln620ln2RA434ln2=Rln (A)

(b) From the mass balance (1) and the acid dissociation constant

, show that

[Hln]=F1nRln+1 (B)

[ln2]=KlnFln[H+](Rln+1) (C)

(c) Show that H+=Kln/Rln (D)

(d) From the carbonic acid dissociation equilibria, show that

[HCO3]=K1[CO(aq)]E[H+][CO32]=K1K2[CO(aq)]F[H+]2

(e) Write the charge balance for the solution in the sensor compartment. Substitute in expressions B, C, E, and F forHln,In2-,[HCO3], and[CO32]

(f) Suppose that the various constants have the following values:

4344HHn=8.00103M1cm1鈥呪赌呪赌呪赌K1=3.01076620Hn=0鈥呪赌呪赌呪赌K2=3.31011434ln2=1.90103M1cm1鈥呪赌呪赌呪赌Kln=2.0107620ln2=1.70104M1cm1鈥呪赌呪赌呪赌Kw=6.71015

From the measured absorbance ratio=2.84, findin the seawater.

(g) Approximately what is the ionic strength inside the sensor compartment? Were we justified in neglecting activity coefficients in working this problem?

Fluorescence quenching in micelles. Consider an aqueous solution with a high concentration of micelles and relatively low concentrations of the fluorescent molecule pyrene and a quencher (cetylpyridinium chloride, designated Q), both of which dissolve in the micelles.


Quenching occurs if pyrene and Q are in the same micelle. Let the total concentration of quencher be [Q] and the concentration of micelles be [M]. The average number of quenchers per micelle isQ=[Q]/[M]. If Q is randomly distributed among the micelles, then the probability that a particular micelle has n molecules of Q is given by the Poisson distribution:

Probability of n molecules of Q in micelle =Pn=Qnn!e-Q

whereis n factorial(=n[n-1][n-2]....[1]). The probability that there are no molecules of Q in a micelle is

Probability ofmolecules of Q in micelle = Pn=Q00!e-Q=e-Q

because 0!=1

Let l0be the fluorescence intensity of pyrene in the absence of Q and let IQbe the intensity in the presence of Q (both measured at the same concentration of micelles). The quotient lQ/l0must be e-Qwhich is the probability that a micelle does not possess a quencher molecule. Substituting Q=[Q]/[M]gives

lQ/l0=e-Q=e-[Q]/[M]

Micelles are made of the surfactant molecule, sodium dodecyl sulfate. When surfactant is added to a solution, no micelles form until a minimum concentration called the critical micelle concentration (CMC) is attained. When the total concentration of surfactant, [S], exceeds the critical concentration, then the surfactant found in micelles is[S]-[CMC]. The molar concentration of micelles is

[M]=[S]-[CMS]Nav

where Nav is the average number of molecules of surfactant in each micelle.

Combining Equationsandgives an expression for fluorescence as a function of total quencher concentration, [Q]:

ln=l0lQ=[Q]Nav[S]-[CMS]

By measuring fluorescence intensity as a function of [Q] at fixed [S], we can find the average number of molecules of S per micelle if we know the critical micelle concentration (which is independently measured in solutions of S). The table gives data for 3.8渭惭

pyrene in a micellar solution with a total concentration of sodium dodecyl sulfate [S]=20.8mM

(a) If micelles were not present, quenching would be expected to follow the Stern-Volmer equation. Show that the graph of l0/lQversus [Q] is not linear.

(b) The critical micelle concentration is 8.1mM.Prepare a graph ofln(l0/lQ)versus [Q]. Use Equation 5 to find Nav, the average number of sodium dodecyl sulfate molecules per micelle.

(c) Find the concentration of micelles, [M], and the average number of molecules of Q per micelle,Q, when[Q]=0.200mM

(d) Compute the fractions of micelles containing,, andmolecules of Q when[Q]=0.200mM

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