= 7.17 A solution of ethanol and n-propanol behaves ideally. Calculate the chemical potential of ethanol in solution relative to that of pure ethanol when its mole fraction is 0.40 at its boiling point I (783°C). Hescas D = Witant + RT ont Cana D+ (8.314 TK"! mol”) (351.5 K) 0.40 nano (©) ~ 2.7 x 10° Jmol“! ‘The chemical potential of ethanol in solution is lower than the chemical potential of pure ethanol by 2.7 x 10° Jmol! 7.21 Acertain dilute solution has an osmotic pressure of 12.2 atm at 20°C. Calculate the difference | between the chemical potential of the solvent in the solution and that of pure water. Assume that the density is the same as that of water. (Hint: Express the chemical potential in terms of mole : fraction, x,, and rewrite the osmotic pressure equation as x V = n,RT, where n is the number of moles of the solute and V = 1 L.) Let the chemical potential of pure water be 11} (0) and the chemical potential ofthe solvent be 1, (). These two chemical potential are related by w, =n} O+ RT Inx, The mole fraction of water, x,, is then calculated from the number of moles of solute, ny, and the number of moles of water, n,, in 1 L of solution. The number of moles of solute is related to the ‘osmotic pressure of the solution. am) 1 L) we 0.5071 mol RT ~ (0.08206 LatmK-* mol) Q95.2K) Since the solution is dilute, the volume of water is assumed to be the same as the volume of the solution and the density of water is assumed to be 1 gem™*, Then _ (1000 em’) (1. gem™) nm : 55.494 mol 18.02 g mol ‘The mole fraction of water is ny 5.494 mol Sc +n, ~ 55.494 mol + 0.5071 mol Substituting x, into the chemical potential expression above, yD = 4j © + (8.314 1K"! mol!) (293.2 K) In (0.9909) = wy (D) ~ 23 ‘The chemical potential of the solution is lower than thst of water by 22.3 J mol”!7.53 Calculate the change in the Gibbs energy at 37°C when the human kidneys secrete 0.275 mole of urea per kilogram of water from blood plasma to urine ifthe concentrations of urea in blood plasma and urine are 0.005 mol kg™! and 0.326 mol kg~!, respectively. ‘The chemical potentials of urea in urine and blood are (Hccea)aine = Hees + RT 10 (ye)ucioe ae) tod = Hire + RT 19 yhoo ‘The change in chemical potential for the kidneys to secret water from blood plasma to urine is (Ha) uiae ~ Hu ions = [Seen + RT 10 (rs) ie ea + RT It (yet son = RP in Cease (adie ‘Since mole fraction is proportional to molality, the above equation can be rewritten as (aes ~ ans = RT 0 ea reais 0.326 m 31 mol”! (8.3143K It ) GOK) no = 1.1 x 10" Smol The change in the Gibbs energy for this secretion process is, AG =n [(Hans aise ~ (Hur rocd) = 0.275 mob (1.1 x 10" Fmol~ | | |7.58 Suppose 2.6 moles of He at 0.80 atm and 25°C are mixed with 4.1 moles of Ne at 2.7 atm and 25°C. Calculate the Gibbs energy change for the process. Assume ideal behavior. | The expression 4,4, = WRT (1 Inx, + ¥;n%) is valid only for mixing two gases originally at i the same pressure and is not directly applicable here. G is a state function, however, so consider a path in which the two gases are first individually brought tothe final pressure of the mixture and then mixed, The overall AG is the sum of the AG’s forthe steps. The process is assumed to take place with the gases originally in swo containers connected by a valve which i opened, The final volume of the mixture is then the sum of the original volumes. Since Ve = “3°, with an similar i expression for Ne, 7 26 mol + 4.1 mol Bathe = 1.41 atm For the compression (expansion) ofan ideal gas, AG = RT In 2,0 that 1 Lal atm AGy, = (2.6 mol) (8.314) K™! mol) (298 K) In = 3.65 x 10? Mt mol") (298 K) In Saye = 3:65 x 10°F AG, = (4.1 mol) (8.314 K™ mol) (298 K) In st Sm 6,60 x 10°F 27am SainF = Meas RT (Spe 1 Xe + Aye Ay) = (26 mol +4.1 mol (8.3143 K mot) 298K) x 2.6 mol In 2.6 mol Témol +4.imol ” (F6mol +4. imal 4.1 mol ( 4.1 mol eee DOL (eee Le TOmol+4.tm0i (Ze mot +4 mai) 1.11 x 108d AG, wat = AGye + AGyg + Ogg = 14 x 1A T = 148.5 A simple way to determine the salinity of water is to measure its conductivity and assume that the conductivity is entirely due to sodium chloride. In a particular experiment, the resistance of a sample solution is found to be 254 ©. The resistance of a 0.050 M KCI solution measured in the same cell is 467, Estimate the concentration of NaCI in the solution. (Hine: First derive an equation relating R to A and c and then use Ag values for A.) According to the solution of Problem 8.1, a relation between the cell constant, c, A, and R is 1 A Act ‘The cell constant is the same for both measurements. Therefore, RKC) _ A(NaCl) e(NaC) R(NaCl) ©“ A(KCI) (KCI) R(KCY) AKC) (KC) eNACD = React ANAC Since the KCI solution is dilute, Ay © A. The NaCl solution is more conductive (less resistive) than the KCI solution, but not too much so, Thus, ‘Ay approximates A for the NaCl solution also. 467: Q 149.85 2°! equiv’ (NaCl) = ( ) [! = em?) (0.050 M) 3542, 126.45 & equiv cm: | | | | | | | | | | | = 011M 88 Calculate the solubility of BaSO, (in gL-') in (a) water and (b) a 6.5 x 1075 solution. The solubility product of BaSO, is 1.1 x 10~"°. Assume ideal behavior M MgSO, ‘The equation for the dissolution of BaSO, is BaSO (s) = Ba**(ag) + $0?-(aq) (a ithe solubility of BsS, i x M, then there arex M of Ba™ and x M SOP the solution. Ky = 11 x 10" = (Ba"*][($02-] = x-x x= 1.05 x 1075 ‘Therefore, The solubility of BaSO, 233.4 g 1.05 x 10-8 matt) ( ) = 25x 107 gL“! Tol (©) The MgSO, solution contains 65 x 10~* M of SOF. Ifthe solubility of BaSO, is x M, then there are x M of Ba” and x + 6.5 x 10S M SO? in the solution a K, +1 107! = BaP] [SOP] =x (x +65 x 10-4) 2746.5 x 10% — 11x 107! 29 165x106 or x = ~6.67 x 10-5 (nonphysical) Therefore, The solubility of BaSO, = (1.65 x 10 mol“) (2348) 39x 10 gL! | |8.14 Calculate the ionic strength and the mean activity coefficient for the following solutions at 298 K: (a) 0.10 m NaCl, (b) 0.010 m MgCl, and (€) 0.10 m K,Fe(CN). ‘The ionie strength can be obtained from the equation 1 2" and subsequently the mean activity from the Debye-Hiickel limiting law 1 logy. = -0.509|c,2.| V7 (a) 0.10 m NaC: z, Shc =—lm, =0.10m,m_=0.10m [0.10 m) (1)? + 0.10 m) (-1)?] = 0.10 m 0.509 |(1) (1)] V0.0 = -0.161 6 (b) 0.010 m Mgt <1, m, = 0.010 m, m. 1 = £[(0.010m) (2 + (0.020 m) (-1) =0.509 |(2) (—1)] 0.030 = -0.176 0.67 (©) 0.10 mK Fe(CNg: 2, = 12, = 4m, 40 m,m_ = 0.10 m 1 = § [00.40 m (1)? + (0.10 m (—8)4] = 1.0m tog, = -0.509 (1) (—4)| VFB 2.04 ye = 9.1 x 107 8.22 The osmotic pressure of blood plasma is about 7.5 atm at 37°C. Estimate the total concentration Of dissolved species and the freezing point of blood plasma. ‘The total concentration of dissolved species is ame 7.5 atm RT Te = 0.295 M = 030M (0.08206 amK=" mol) Gio) ~ 075M = 030 Assuming that molality can be approximated by molarity, the freezing point depression caused by the dissolved species is AT = Kym, = (1.86 Kmol~ kg) (0.295 mol kg) 55K ‘Therefore, blood plasma freezes at ~0.55°C or 272.60 K.I EEEEEEEEEEEISSES'S:”’*CS§ ~~ a and Nat cers tzations are 20 mAf and 440 mi, respectively. Given that the electric potential inside the ellis ~70 mv relative tothe outside, calculate the Gibbs energy change forthe wana of each type of ion against the concentration gradient at 37°C. ——— In-each case the Gibbs energy change going against the concentration gradient is found using fer of 1 mole KH SG=2TIn we +2F AY, Note that 1 V = 1 C7! Fork* 1K, AG = RT in he nga teFAV | _ ao 400 mu | = (8314K my (8.3143 K~! mol") (310 K) In mat * () (96500 Cmot~) (0.070 vy | = 966 Jmol"! = 0.97 kt mol! For Na (Net, AG = RT nou ee PAY = (83145 K" mol) 310%) in 30 mi = 1.24 x 108 Jmol™! = 12 kJ mol-! 440.mM + (1) (96500 Cmol~') (+0.070 vy Although the concentration gradients ae similar, it is easier to transport K* ions into the cel since they are going towards a negative electric potential, than to t y tric potential, than to transport Na* ions outside the cell towards a positive potential : omisess i 8.28 (a) The root cells of plants contain a solution that is hypertonic in relation to water in the soil ‘Thus water can move into the roots by osmosis. Explain why salts (NaCl and CaCl,) spread on roads to melt ice can be harmful to nearby trees. (b) Just before urine leaves the human body, the collecting ducts in the kidney (which contain the urine) pass through a fluid whose salt concentration is considerably greater than is found in the blood and tissues. Explain how this action helps to conserve water in the body. (a) When the road salts get into the soil water, the concentration there becomes greater than the concentration in the plant root cells, making the solution in the cells hypotonic. Thus the osmotic pressure difference will be reversed, and water will flow out of the plant roots into the soil. This action is harmful and potentially fatal to the plant. Even if the effect is not as severe, there will be a reduction in the osmotic pressure, which will limit the height to which the water can rise in the plant (b) The high-salt fluid is hypertonic relative to urine, Thus, some of the water in the urine flows into the fluid by osmosis. This action concentrates the waste products in the urine and helps to conserve water in the body.