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Inorganic : detergent
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 Message 1 of 5 in Discussion 
From: MSN NicknameXenonPrincessWarrior  (Original Message)Sent: 3/13/2006 4:32 PM
Hi,
An aqueous solution contains 1.00 g of a detergent per liter of water.  The osmotic pressure of the solution at 25.0 ºC is 17.8 mmHg.  Calculate the molar mass of the detergent assuming it consists of a single particle when dissolved.
 
How would you set up this problem? Thanks.


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Reply
 Message 2 of 5 in Discussion 
From: MSN Nickname·Steve·Sent: 3/13/2006 10:03 PM
You can break it down into three steps:

1.  Calculate M from the osmotic pressure formula  P  =  MRT
2.  Calculate moles from the molarity formula  M  =  moles / Liter
3.  Calculate M (the molar mass) from  moles  =  grams / M

In step 1, convert the osmotic pressure P to atmospheres and use R  =  0.08206 L atm / mol K (and of course convert T to Kelvin).
 

Steve

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 Message 3 of 5 in Discussion 
From: MSN NicknameXenonPrincessWarriorSent: 3/18/2006 9:40 PM
So is this the final answer?
 
I am confused about the part that says assuming it consists of a single particle when dissolved.
 osmo.doc  

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 Message 4 of 5 in Discussion 
From: MSN Nickname·Steve·Sent: 3/19/2006 9:00 AM

Everything's OK except where you calculated moles of solute from the molarity - that will be  moles  =  V in liters  X  molarity  rather than dividing the molarity by the volume.  Since the volume was 1 L, it didn't affect your answer.
Nice job showing the units also.


>>  I am confused about the part that says assuming it consists of a single particle when dissolved.  <<

When doing colligative property calculations, you always have to calculate the moles of solute "particles" rather than simply the moles of solute only.  For example, when NaCl is dissolved in water you get two particles, an Na+ ion and a Cl- ion.  So in a colligative property calculation of a solution of NaCl (the vapor pressure, boiling point, freezing point, or osmotic pressure) you would multiply the moles of NaCl by two to get the moles of particles.  That is the number of moles you would use in each of the colligative property formulas.

Unfortunately this problem was not realistic because common synthetic detergents are salts of sulfonic acids, such as sodium p-dodecylbenzenesulfonate, Na+ -OSO2--C6H4--(CH2)11CH3.  This gives two particles just like NaCl does, and even though the two detergent ions are very different from each other, ideally they behave the same with regard to colligative properties.

In your calculation, the way we would correct for this would be, knowing that each mole of detergent gives two ions in solution, to divide the moles calculated from the osmotic pressure by two.  That would give simply the moles of detergent "formulas units" NaA, where A- is the anion (and Na+ is the assumed cation).  Your calculated molecular weight would double.  Maybe because of this confusion, the problem was simplified so that the number of solute particles was not a factor.  If the solute was molecular (rather than ionic) then the original calculation would be correct, because molecular solutes like sugar only give one solute particle when they dissolve.


Steve


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 Message 5 of 5 in Discussion 
From: MSN Nickname·Steve·Sent: 3/20/2006 4:37 AM
>>  assuming it consists of a single particle when dissolved  <<
 
It may be in the case of soaps and detergents that significant ion-pairing occurs.  This is when a positive and negative ion in solution come in contact, behaving for a brief time as a single solute particle.  Ion-pairing in solutions of ionic compounds increases with concentration, and as a result considerable deviation from the colligative property formulas occurs.  The concentration of ions divided by the concentration of dissolved solute is called the van't Hoff factor, i.  Here are van't Hoff factors for MgSO4 (which gives two ions in solution):

Molal concentration                            i       
0.1 m                                              1.21
0.01 m                                            1.53
0.001 m                                          1.82
 
If 100% dissociation occurs               2

Even at the fairly dilute concentration of 0.1 m (m = moles of solute / kg of solvent) MgSO4 behaves more like one particle than two.  The Mg2+ and SO42- ions really attract each other.  NaCl is not as bad as this, since the ions have charges of only +1 and -1 and so do not attract each other as strongly (i = 1.87 at 0.1 m, not so far from the ideal value of 2).

Soaps and detergents have a long, nonpolar hydrocarbon "tail" part which is hydrophobic and therefore does not interact with the water solvent molecules well.  This can increase the ion-pairing effect because if the ion containing the nonpolar part (the negative ion) does not dissolve easily, the positive ion (such as Na+) cannot get very far away.

So possibly soaps and detergents really do behave more like one particle in solution due to this ion-pairing, rather than the expected two particles.  If so, the problem is being realistic in this regard.

Nothing is ever "simple" in chemistry!
 
 
Steve

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