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Calibration of a glass electrode gave a reading of 139.7 mV with saturated potas

ID: 918750 • Letter: C

Question

Calibration of a glass electrode gave a reading of 139.7 mV with saturated potassium hydrogen tartrate buffer standard (pH = 3.557) and a reading of -92.2 mV with 0.08 m HEPES, 0.08 m NaHEPES, 0.08 m NaCl buffer standard (pH = 7.454), both measured at 30°C.

(a) What is the observed slope (mV/pH unit) of the calibration curve?

(b) What is the theoretical slope at 30°C?

(c) What is , the electromotive efficiency to three significant figures?? Open the hint panel below for the definition of electromotive efficiency.

(d) What is the pH of an unknown that gives a reading of 46.9 mV with this electrode at 30°C?

Explanation / Answer

a.

Slope S = dE/dpH = (139.7-(-92.2))/(3.557-7.454) = - 231.9/3.897= - 59.51 mV/pH unit

b. The theoretical slope is

          -2.303RT/nF

    The known value at 298 K is - 0.05916 V (see Nernst equation)

     The value at 303 K is

        -0.05916 V x303K/298K = -0.06015 V = -60.15 mV/pH unit

c.

59.51 mV/pH / 60.15 mV/pH = 0.9893

d.

pHx = pH + (Ex-E)/S      

                                          (pH and E, any known pair, look also at a., same equation)

                = 7.454 - (46.9 + 92.2)/ 59.51

                = 7.454 – 2.337 = 5.117

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