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Osmotic pressure measurements can be used to determine the molecular weights of large molecules such as proteins. For a solution of large molecules to qualify as "dilute," its molar concentration must be very low and hence the osmotic pressure can be too small to measure accurately. For this reason, the usual procedure is to measure the osmotic pressure at a variety of concentrations, then extrapolate the results to the limit of zero concentration. Here are some data for the protein hemoglobin dissolved in water at 3oC:

Concentration (grams/liter)∆h (cm)
5.62.0
16.66.5
32.512.8
43.417.6
54.022.6

The quantity ∆his the equilibrium difference in fluid level between the solution and the pure solvent,. From these measurements, determine the approximate molecular weight of hemoglobin (in grams per mole).

An experimental arrangement for measuring osmotic pressure. Solvent flows across the membrane from left to right until the difference in fluid level,∆h, is just enough to supply the osmotic pressure.

Short Answer

Expert verified

The approximate molecular weight is 66.3kg/mol.

Step by step solution

01

Step 1. Given Information

We are given a table,

02

Step 2. The osmotic pressure 

For dilute solutions, the osmotic pressure can be approximated as,

Ï€=nRTV

Ï€=nRTV=cRTM

Therefore,

M=cRTÏ€

Here the number density of the solute nVin moles/liter is replaced by cM, cis the concentration of the solute in (grams/liter) and Mis its molecular weight (in grams/mole). But in this experiment the osmotic pressure is balanced by the difference in the fluid level ∆hso for each solute concentration, one can calculate the osmotic pressure by the following formula,

Ï€=Òϲµâˆ†h

Substitute ÒÏg∆hfor Ï€in the equation M=cRTÏ€

Ï€=nRTV=cRTM

Use the density of water ÒÏ=1g/cm3. The table given below shows the value of the osmotic pressure for each solute condition and the corresponding estimated value of the molecular weight from the following relation,

03

Step 3. Consider the following table,

The table is as follows,

Concentration
grams/liter=kg/m3
∆hcm
Ï€N/m2
Mkg/mole
5.62.0196.265.5
16.60.5637.659.7
32.512.81255.759.4
43.417.61726.657.7
54.022.62217.155.9
04

Step 4. Graph of concentration versus molecular mass

The graph of concentration versus molecular mass is as follows,

05

Step 5. Approximated Molecular Weight

The molecular weight estimated from each measurement is plotted versus the concentration. As the equation that relates osmotic pressure to the concentration of solutes is most accurate in the limit of very dilute solution, one should extrapolate the results to zero concentration. If apparently one bad point at c=16.6g/Lis ignored, the molecular weight is M=66.3kg/mol. Therefore, the approximate molecular weight is66.3kg/mol

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Most popular questions from this chapter

Plot the Van der Waals isotherm for T/Tc = 0.95, working in terms of reduced variables. Perform the Maxwell construction (either graphically or numerically) to obtain the vapor pressure. Then plot the Gibbs free energy (in units of NkTc) as a function of pressure for this same temperature and check that this graph predicts the same value for the vapor pressure.

A formula analogous to that for CP-CVrelates the isothermal and isentropic compressibilities of a material:

κT=κS+TVβ2CP.

(Here κS=-(1/V)(∂V/∂P)Sis the reciprocal of the adiabatic bulk modulus considered in Problem 1.39.) Derive this formula. Also check that it is true for an ideal gas.

Everything in this section so far has ignored the boundary between two phases, as if each molecule were unequivocally part of one phase or the other. In fact, the boundary is a kind of transition zone where molecules are in an environment that differs from both phases. Since the boundary zone is only a few molecules thick, its contribution to the total free energy of a system is very often negligible. One important exception, however, is the first tiny droplets or bubbles or grains that form as a material begins to undergo a phase transformation. The formation of these initial specks of a new phase is called nucleation. In this problem we will consider the nucleation of water droplets in a cloud. The surface forming the boundary between any two given phases generally has a fixed thickness, regardless of its area. The additional Gibbs free energy of this surface is therefore directly proportional to its area; the constant of proportionality is called the surface tension, α

σ≡GboundaryA

ff you have a blob of liquid in equilibrium with its vapor and you wish to stretch it into a shape that has the same volume but more surface area, then u is the minimum work that you must perform, per unit of additional area, at fixed temperature and pressure. For water at 20°C,σ=0.073J/m2

(a) Consider a spherical droplet of water containing N1 molecules, surrounded by N-N1molecules of water vapor. Neglecting surface tension for the moment, write down a formula for the total Gibbs free energy of this system in terms of N,N1, and the chemical potentials of the liquid and vapor. Rewrite N1in terms of V1, the volume per molecule in the liquid, and T, the radius of the droplet.

(b) Now add to your expression for Ga term to represent the surface tension, written in terms of Tand u.

(c) Sketch a qualitative graph of G vs. T for both signs of µg - µ1, and discuss the implications. For which sign of μg-μ1does there exist a nonzero equilibrium radius? Is this equilibrium stable?

(d) Let TCrepresent the critical equilibrium radius that you discussed qualitatively in part (c). Find an expression for TCin terms of μg-μ. Then rewrite the difference of chemical potentials in terms of the relative humidity (see Problem 5.42), assuming that the vapor behaves as an ideal gas. (The relative humidity is defined in terms of equilibrium of a vapor with a flat surface, or with an infinitely large droplet.) Sketch a graph of the critical radius as a function of the relative humidity, including numbers. Discuss the implications. In particular, explain why it is unlikely that the clouds in our atmosphere would form by spontaneous aggregation of water molecules into droplets. (In fact, cloud droplets form around nuclei of dust particles and other foreign material, when the relative humidity is close to 100%.)

Derive a formula, similar to equation 5.90, for the shift in the freezing temperature of a dilute solution. Assume that the solid phase is pure solvent, no solute. You should find that the shift is negative: The freezing temperature of a solution is less than that of the pure solvent. Explain in general terms why the shift should be negative.

The methods of this section can also be applied to reactions in which one set of solids converts to another. A geologically important example is the transformation of albite into jadeite + quartz:

NaAlSi3O8⟷NaAlSi2O6+SiO2

Use the data at the back of this book to determine the temperatures and pressures under which a combination of jadeite and quartz is more stable than albite. Sketch the phase diagram of this system. For simplicity, neglect the temperature and pressure dependence of both ∆S and ∆V.

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