Tag Archives: Chemistry

Choosing an Acetophenetidin Solvent

When synthesizing Acetophenetidin (Phenacetin) in an Organic Laboratory, you might end up with a cake of crude product filled with impurities from the synthesis process.  A giveaway sign of this is a calculated percent yield in excess of one hundred percent.  This is not high-quality product.  It must be recrystallized in order to refine the product for larger crystals and purer yield.

In order to recrystallize a product for better purity, a solvent must be found that will solvate everything at high temperatures, but will precipitate the pure product at cooler temperatures while keeping the impurities solvated and out of the crystal structure of the reforming product.

Perhaps you are given three options: deionized water, ethanol, and hexane.  To test which would be the better solvent, add a bit of the crude product to small amounts of the potential solvents in test tubes.  Observe solubility.  Then heat the solvents in a boiling hot-water bath and observe solubility at that state.  Finish the mock recrystallization by removing the test tubes from the bath and letting them cool to room temperature before sticking them in an ice bath.  Observe solubility once again.

The better solvent will preferably not solvate the acetophenetidin at room temperature.  This means that the recrystallization will begin earlier in the cooling phase.  Everything must be dissolved at boiling.  A solvent with a low boiling point would not help here, as it will evaporate away leaving everything as an impure solid stuck to the sides of the test tube.  When cooled in ice, crystals must form for the solvent to be worth anything.

Here is some sample data:


  • Room Temperature – Crude product appeared to be insoluble
  • Boiling – Completely solvated the crude product
  • Freezing – Crystals reappeared


  • Room Temperature – Completely solvated
  • Boiling – Still solvated
  • Freezing – Remained solvated


  • Room Temperature – Insoluble
  • Boiling – Solvent evaporated
  • Freezing – The solvent evaporated away in the previous step

The hexane is out as a solvent; its boiling point is too low.  Ethanol does not work because the acetophenetidin never precipitates out of it.  This leaves only water, and the observations associated with it prove it to be a useful solvent.

It is important to know what to look for when observing the Freezing solubility.  Even though the impure cake may enter the test tube as a lump, it will not precipitate that way.  Once the test tubes are sitting in the ice bath, let them sit undisturbed for five minutes.  Then remove and observe.  Wipe the condensation off the tubes and look very closely at them.  From farther away, the water and ethanol tubes look much the same.  Upon closer inspection and perhaps a swirl, one can see very tiny white particles floating in the water that are absent in the ethanol.  That is the pure acetophenetidin and a good sign.  These particles may be even smaller than any dust in the tube; close observation is important here.


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Getting Tripped By Markovnikov

Markovnikov’s rule is a decent tool to predict some simple organic reactions. It states that in simple electrophilic additions of alkenes, such as Hydrogen Chloride to n-Pentene, the electrophile will attach itself to the carbon of the double bond that has more Hydrogen atoms already attached; the less substituted carbon. It can trip a user up, however, if they do not understand the actual process taking place. Example:


1-phenyl-2-methylpropene has two “sp2” hybridized carbons in its Propene backbone. In a reaction with Hydrogen Chloride, we will only consider these two points and will leave out attachments to the Benzene ring itself for simplicity.

When the PI bond reattaches itself to a passing Hydrogen (HCl), it creates an intermediate carbocation and a Chloride ion. Which of the two carbons the intermediate forms on is determined by stability considerations. Markovnikov’s rule would predict the hydrogen attaching to the Phenyl side, as there is only one substituent there. The reverse actually happens, creating a “non-Markovnikov” scenario where the Chloride ion attaches to the molecule close to the Phenyl substituent.

Instead of relying on Markovnikov’s rule for simple additions which create carbocations, use the idea of hyperconjugation. This boils down to the idea that carbocations (positively charged) can be stabilized by the sigma bonds of nearby substituents (usually carbon to hydrogen bonds) because the electrons involved in sigma bonding are negatively charged. The more substituents, the more stabilized a present carbocation becomes. The stability of carbons with positive charges becomes:

1^{\circ} < 2^{\circ} < 3^{\circ}

Primary carbocations are less stable than tertiary because tertiary carbocations have two more sets of hyperconjugation sigma bonds to stabilize the positive charge.

However, sigma hyperconjugation is nowhere near as stabilizing as the effects of lone pairs of nearby electrons such as those found in “sp2” hybridized carbons. The negative charge is less diluted in the lone pair. This makes Allyl and Benzene groups even more effective than tertiary carbons. The order stands at:

1^{\circ} < 2^{\circ} < 3^{\circ} < Allyl < Benzene

The point of this is that when a carbocation intermediate forms, it will form in the most probable place most of the time. The most probable is the most stable. Carbocations will form on carbons attached to Benzene before they attach to carbons with only two other carbons (methyl groups, for instance) attached to themselves.

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Silver Phosphate and Acetic Acid

Silver phosphate has the formula:


Acetic Acid has the formula


Mix them together and you get the equation:

Ag_{3}PO_{4(s)} + 3\; CH_{3}COOH_{(aq)} \rightleftharpoons 3\; AgCH_{3}COO_{(s)} + H_{3}PO_{4(aq)}

The equilibrium equation from this formula is:

\kappa = \frac{[H_{3}PO_{4}]}{[CH_{3}COOH]^3}

To compute the equilibrium constant from this, multiply by values that are equal to one, but that allow you to use known constants:

\kappa = \frac{[H_{3}PO_{4}]}{[CH_{3}COOH]^3} * \frac{[H_{3}O^{+}]^3}{[H_{3}O^{+}]^3} * \frac{[CH_{3}COO^{-}]^3}{[CH_{3}COO^{-}]^3} * \frac{[Ag^{+}]^3}{[Ag^{+}]^3} * \frac{[HPO_{4}^{2-}]}{[HPO_{4}^{2-}]} * \frac{[PO_{4}^{3-}]}{[PO_{4}^{3-}]}

\kappa = \frac{(\kappa _{a(CH_{3}COOH)})^3 * \kappa_{sp(Ag_{3}PO_{4})}}{(\kappa _{sp(AgCH_{3}COO)})^3 * \kappa _{a(H_{2}PO_{4} ^{-})} * \kappa _{a(HPO_{4}^{2-})}}

\kappa = \frac{(1.8\cdot 10^{-5})^{3}(1.3\cdot 10^{-20})}{(2.0\cdot 10^{-3})^{3}(6.3\cdot 10^{-8})(4.2\cdot 10^{-13})}

\kappa = \frac{[H_{2}PO_{4}^{-}]}{[CH_{3}COOH]^2} =5.0\cdot 10^{-5}

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