Ch. 2 - Molecular RepresentationsWorksheetSee all chapters
All Chapters
Ch. 1 - A Review of General Chemistry
Ch. 2 - Molecular Representations
Ch. 3 - Acids and Bases
Ch. 4 - Alkanes and Cycloalkanes
Ch. 5 - Chirality
Ch. 6 - Thermodynamics and Kinetics
Ch. 7 - Substitution Reactions
Ch. 8 - Elimination Reactions
Ch. 9 - Alkenes and Alkynes
Ch. 10 - Addition Reactions
Ch. 11 - Radical Reactions
Ch. 12 - Alcohols, Ethers, Epoxides and Thiols
Ch. 13 - Alcohols and Carbonyl Compounds
Ch. 14 - Synthetic Techniques
Ch. 15 - Analytical Techniques: IR, NMR, Mass Spect
Ch. 16 - Conjugated Systems
Ch. 17 - Aromaticity
Ch. 18 - Reactions of Aromatics: EAS and Beyond
Ch. 19 - Aldehydes and Ketones: Nucleophilic Addition
Ch. 20 - Carboxylic Acid Derivatives: NAS
Ch. 21 - Enolate Chemistry: Reactions at the Alpha-Carbon
Ch. 22 - Condensation Chemistry
Ch. 23 - Amines
Ch. 24 - Carbohydrates
Ch. 25 - Phenols
Ch. 26 - Amino Acids, Peptides, and Proteins

Now that we understand how bonds keep atoms together, the next question is, what force keeps molecules together? Do they bond to each other as well? Let’s take a look. 

Concept #1: How IMFs are related to melting and boiling points.  

Transcript

Let's talk about intermolecular forces. Intermolecular forces are forces that exist between molecules, not within the molecules. If it's within a molecule, that's actually just called a chemical bond. That would be like one atom attached to another atom. But with intermolecular forces what I'm talking about is one molecule that is loosely associated with another molecule meaning they just like to stick together a little bit.
It turns out that IMFs are what make molecules sticky. I know that that kind of sounds weird that molecules would be sticky, but they actually are. It turns out that if these molecules did not stick together in some way, everything in the universe would be a gas. In order to have solids, in order to have liquids, these molecules have to aggregate. They need to remain somewhat close to each other or they're just going to disperse.
That's what intermolecular forces do. They don't actually change the compound, the compound is affected by bonds, but the way that the state of the matter is affected by intermolecular forces.
I just want to show you guys this really quick diagram. This shows you three different molecules that have about the same molecular weight. Theoretically, if they have the same molecular weight, you would think that overall the type of substance would be similar, but actually, it turns out to be very different.
Here we have a three-carbon atom. I said atom; I meant molecule. Sorry. Here we have a two-carbon molecule with one oxygen. And here I also have a two-carbon molecule with one oxygen. These are very similar looking molecules and they're very similar shapes and yet their boiling points are vastly different.
If you look at propane, propane is like a propane gas. Why do we keep it in a gas tank? Because it's gas. There's no way that you could just put propane in a bowl or in a cup. It would immediately turn into gas.
Then we have dimethyl ether which just by adding one oxygen in that location, we've increased the boiling point a little bit. Remember that ether is one of those reagents that you're going to use a lot in the lab and remember that it's very reactive. And one of the reasons is because it turns into a gas very easily, so it's very volatile.
Then the last one here is ethanol. I've brought up ethanol before. You guys are very familiar with it. That's like vodka. If your vodka was a gas, it probably wouldn't be as easy to consume. But it turns out that ethanol doesn't boil until 173 degrees Celsius.
That's crazy. Look how much different this boiling point is from this one. What's the difference? Why is it such a much higher boiling point? Why does ethanol exist as a liquid in room temperature, whereas propane and dimethyl ether are going to exist as a gas? The reason has to do with intermolecular forces.
Whenever you get questions about boiling points or melting points, that's the way that professors like to ask these questions, it always has to do with the strength of IMFs between molecules. So if a professor ever asks you list the following molecules in order of increasing boiling point or something like that, you know that they're talking about IMFs. 

*Correction: The bp (boiling point) of "Ethanol" is 173˚ F or 78˚ C

All these molecules have similar molecular weights; however they have vastly different boiling points. Why is that?

 

Intermolecular forces (IMF’s) keep molecules stuck together. Questions about boiling / melting points of molecules are always referring to the strength of IMF’s between molecules. 

Strength of IMF's
  1. Hydrogen bonding

Hydrogens attached to small, highly electronegative atoms can hydrogen bond. Namely N, O and F. 

Concept #2: How hydrogen bonding works. 

Transcript

So there's three main intermolecular forces that we want to know and I'm going to teach you them in order from strongest to weakest. So we're going to start with the strongest, most important intermolecular force and then we're going to end off with the weakest one.
The strongest one is H-bonding, hydrogen bonding. You guys learned about this in gen chem. Maybe you guys can tell me which atoms are the ones that are able to hydrogen bond? Do you remember? It was small, highly electronegative. That was N, O and F. These are the three atoms that if they're attached to an H, they're able to hydrogen bond.
The way that hydrogen bonding works is that, for example, it keeps water together. Water is here. And then what you wind up getting is that another water molecule gets close and between one of the O's and one of the H's you end up getting a loose – actually a pretty tight interaction. And that interaction is called hydrogen bonding.
Now this one's drawn a little bit weird, but you can see that pretty much every O can interact with an H and every H can interact with an O pretty much. They can all arrange themselves tightly together. That's what keeps molecules like water, like ethanol, that's what keeps them as liquids because they're able to get really close to each other and interact and attract each other.
Hydrogen bonding is going to be the most important intermolecular force. If any molecule has this force, we're going to say that that one is going to have the highest boiling point or the highest melting point or whatever. 

  1. Dipole-dipole

We like to call this the net dipole force because it’s only present when the molecule has a net dipole. 

Concept #3: How dipole-dipole forces work.

Transcript

So now let's go to the second most important, the second strongest, and that's the thing we call the dipole-dipole force or what I like to call the net dipole force. Why? Because if you know how to draw dipoles and if you know how to find net dipoles, that's all you need for this.
For example, a molecule like acetone, which is one that I brought up earlier in our lessons, acetone looks like this. Does it have a dipole? Yes, it does. It actually has several dipole moments. It would have dipole moments pulling this way and this way because of the lone pairs. And it would have a major dipole moment pulling that way because of the double bond, but overall we would just say that it has basically a partial negative up here and a partial positive down here.
Does that make sense so far? Because basically, what's going to end up happening is that I'm just going to get a big dipole pulling electrons, oops. I'm going to get a big dipole pulling electrons towards the O. So I'm going to get a partial negative and a partial positive. Remember that we use the lower case delta to represent partial and it means that I don't know exactly what the number is, I just know that it's more than the other.
Well, check out what can happen. When I have a net dipole, another acetone molecule can arrange itself so that the partial negative from one of the molecules orients with the partial positive of the other and in that way they wind up sticking together. And you can imagine that I could have a bunch of acetone molecules all neatly arranged so that all the negatives link with all the positives. This is only possible though if you have a net dipole. If there's no net dipole, then you're not going to be able to form this force. Does that make sense?
So this is what we call the second strongest force. It's not quite as strong as hydrogen bonding, but it still is a pretty strong force. 

  1. Van der Waals Forces
  • Also known as London Dispersion Forces or Dipole-Induced Dipole Forces

All molecules possess Van der Waals Forces. They increase with the following properties:             

  1. Size (the heavier, the stronger the force)
  2. Shape: Ring > Straight Chains > Branched Chains

This picture is trying to illustrate how rings have greater surface area for interactions than straight or branched chains. 

Concept #4: How Van der Waals forces work.

Transcript

So then we move on to our last one which is our weakest force and it turns out that all molecules contain this force. Oops. All molecules possess Van der Waals. So I'm just going to put Van der Waals. But they don't all possess it to the same extent. What that means is that some molecules are going to have higher Van der Waals and some are going to have lower.
What makes Van der Waals' forces increase? The very first thing and most important thing is the size and that has to do with the molecular weight of the molecule. The higher the molecular weight, the stronger the Van der Waals. Pretty easy, right? Cool.
Then we've got the second most important thing or the second indicator is going to be the shape, the shape of the molecule. The shape has to do with how neatly they can be arranged and how neatly they can be ordered.
So what I'm going to do here is I'm going to draw three different molecules and you tell me which one would have the highest Van der Waals force. Here I've got a ring that's a six-membered ring. Here I've got a six-membered chain and then here I've got another six-membered chain. What I want to know is out of these three, which of them is going to have the highest Van der Waals.
First of all what we would look at is the size. Are all the sizes the same? Yes, they all have six carbons, so actually, in terms of size, they're fine.
Then I would look at the shape. Which one has the shape that can arrange the neatest and can stack the best? And the answer is the ring because check it out. The ring, since it's so symmetrical, it can have a bunch of rings stacked on top of each other. So if I wanted, I could keep drawing these rings stacked on top of each other. Do you know what that means? That there's intermolecular Van der Waals' forces all in between that keeping them stuck together. Does that make sense so far?
Then with the chains, the chains are still pretty good, but they're not quite as good as the ring. So here I'm drawing an example of Van der Waals' forces here. These are okay, but they're not quite as good as the rings. Does that make sense?
Then finally, you've got the branch, which I'll try to move out of the way because I know that it's right on top of me. But with the branch what we find is that there's not really a great way for them to stack together. They wind up kind of having a lot of space in between them. Does that make sense? So the Van der Waals' forces here are going to be very small compared to the Van der Waals' forces here for the rings. Does that make sense? Cool.
Basically, I hope that this clarifies intermolecular forces. The first thing to look for is the type of force. Hydrogen bonding is the best, Van der Waals is the worst, dipole is in the middle. And then we kind of break it down from there.
So now what I want to do is do a few practice problems so you guys get comfortable with this and I'm going to try and trick you a little bit, so be prepared. All right? Let's go. 

Practice Questions: Now that we have learned about factors that influence the strength of IMF's let's apply them!

Practice: PRACTICE: Which of the following pairs of molecules would have the highest boiling point?

Practice: PRACTICE: Which of the following pairs of molecules would have the highest boiling point?

Practice: PRACTICE: Which of the following pairs of molecules would have the highest boiling point?

Practice: PRACTICE: Which of the following pairs of molecules would have the highest boiling point?

Which compound in each of the following pairs would have the higher boiling point? Explain your answers.  
Which compound in each of the following pairs would have the higher boiling point? Explain your answers.
Which compound in each of the following pairs would have the higher boiling point? Explain your answers.  
Which compound in each of the following pairs would have the higher boiling point? Explain your answers.  
Which compound in each of the following pairs would have the higher boiling point? Explain your answers.
Which compound in each of the following pairs would have the higher boiling point? Explain your answers.  
Which compound in each of the following pairs would have the higher boiling point? Explain your answers.
The IR spectrum of propanoic acid (Fig. 2.17) indicates that the absorption for the      O - H stretch of the carboxylic acid functional group is due to a hydrogen-bonded form. Draw the structure of two propanoic acid molecules showing how they could dimerize via hydrogen bonding.
Circle the compound with the highest boiling point: a) CH4 b) CH3CH3 c) CH3Cl d) CH3Br e) CH3OH
Without referring to tables, decide which member of each of the following pairs would have the higher boiling point. Explain your answers. (a) Pentane or 2-methylbutane  
Without referring to tables, decide which member of each of the following pairs would have the higher boiling point. Explain your answers. (b) Heptane or pentane  
Without referring to tables, decide which member of each of the following pairs would have the higher boiling point. Explain your answers. (c) Propane or 2-chloropropane  
Without referring to tables, decide which member of each of the following pairs would have the higher boiling point. Explain your answers. (d) Butane or 1-propanol  
Without referring to tables, decide which member of each of the following pairs would have the higher boiling point. Explain your answers. (e) Butane or CH3COCH3  
Which of these compounds would have the  highest boiling point? a. I b. II c. III d. IV  
Describe all the intermolecular interactions in low molecular weight alcohol. Draw out your alcohols chemical structure and use pictures and bullet (brief) points to describe these interaction. 
Rank the following compounds from lowest to highest boiling point. diethyl ether      1,2-propanediol      1-butanol
Which compound has the lower boiling point? a) CH3(CH2)2CH3 or b) (CH3)2CHCH2CH3
Which compound has the higher boiling point: a) CH3(CH2)3CH3 or b) (CH3)4C
Most people are familiar with the idea that oil and water do not mix. Crude oil is a complex mixture of mostly very long chain alkanes. During the refining process, the long alkane chains of crude oil are broken into shorter chains using heat and catalysts, then purified by distillation at refineries on the basis of boiling point into fractions such as gasoline (boiling point fraction between 100°C and 400°C) or diesel fuel (boiling point fraction between 180°C and 360°C). During the Deepwater Horizon oil rig disaster a little over two years ago, between 17 and 39 million gallons of crude oil spilled into the Gulf of Mexico. Thousands of birds, turtles and sea mammals died because they were covered by oil. Well over 125 miles of coastline were affected. The major cause of the destruction is that the oil was not simply diluted by sea water, but rather, it floated on the surface in large slicks that were blown by prevailing winds until they reached a shore. What is worse, animals that need to breath air such as turtles and sea mammals (dolphins, whales, manatees) became trapped under the oil slick and had to surface into it to breathe, sealing their doom. Unsuspecting birds landed on the surface of the oil slick, becoming covered in sticky oil that prevented them from flying away. Why does oil float on the surface of sea water rather than sink to the bottom? A. Oil is less dense than water primarily because crude oil is mostly -CH 2- chains while water is H2O and O has a higher atomic number than C. B. Oil is less dense than water primarily because crude oil is mostly -CH 2- chains while water is H2O and O has a lower atomic number than C. C. Oil is less dense than water primarily because water molecules cannot pack together as well as the crude oil molecules pack together. D. All of the above. The long chain alkanes of crude oil stick to each other largely through interactions that can be described as the following: A. London dispersion forces. B. Attraction between induced transient dipoles associated with temporary fluctuations in electron clouds around the molecules. C. Hydrogen bonding D. Both A and B
Most people are familiar with the idea that oil and water do not mix. Crude oil is a complex mixture of mostly very long chain alkanes. During the refining process, the long alkane chains of crude oil are broken into shorter chains using heat and catalysts, then purified by distillation at refineries on the basis of boiling point into fractions such as gasoline (boiling point fraction between 100°C and 400°C) or diesel fuel (boiling point fraction between 180°C and 360°C). During the Deepwater Horizon oil rig disaster a little over two years ago, between 17 and 39 million gallons of crude oil spilled into the Gulf of Mexico. Thousands of birds, turtles and sea mammals died because they were covered by oil. Well over 125 miles of coastline were affected. The major cause of the destruction is that the oil was not simply diluted by sea water, but rather, it floated on the surface in large slicks that were blown by prevailing winds until they reached a shore. What is worse, animals that need to breath air such as turtles and sea mammals (dolphins, whales, manatees) became trapped under the oil slick and had to surface into it to breathe, sealing their doom. Unsuspecting birds landed on the surface of the oil slick, becoming covered in sticky oil that prevented them from flying away. As mentioned in the passage, when crude oil is refined, heat and catalysts break the long carbon chains into much shorter ones. The resulting mixture is distilled and fractions with specific boiling point ranges are collected together and sold according to their intended use such as jet fuel, gasoline, heating oil, etc. Based upon what you know about the boiling points of branched vs. straight chain alkanes, which statement do you think will NOT be true as you analyze what actual molecules are in each fraction isolated based on similar boiling points. A. The fractions with higher boiling points will generally have larger alkane molecules (higher molecular weights). B. In a given fraction, the branched molecules will on average have a higher molecular weight compared to the straight chain molecules. C. In a given fraction, the branched molecules will on average have a lower molecular weight compared to the straight chain molecules.  D. The fractions with lower boiling points will generally have smaller alkane molecules (lower molecular weights).
Rank the following compounds from lowest to highest boiling point.
We have seen in this chapter that, among isomeric alkanes, the unbranched isomer is the least stable and has the highest boiling point; the most branched isomer is the most stable and has the lowest boiling point. Does this mean that one alkane boils lower than another because it is more stable? Explain. 
Please follow the steps below: A) Construct the Kekule or Lewis-Dash (including lone pairs) for the following molecule. B) Use dipole arrows to denote any polar bonds. C) Is the molecule polar? D) What is the strongest intermolecular force present? CH2CHCO2H Circle one: Polar molecule? Yes or no Strongest IMF: _________________
Please follow the steps below:
The structural unit below has been incorporated into a synthetic polymer designed to mimic the skeletal muscle protein titin (J. Am. Chem. Soc. 2009, 131, 8766–8768). In its most stable conformation (not the one shown), it forms one intramolecular hydrogen bond and four intermolecular hydrogen bonds to an identical unit in the same conformation. Draw two equivalents of this molecule and clearly show all of the interactions described above.
For each pair of compounds below, predict which compound will have the higher boiling point and explain your choice:  (a) CH3CH2CH2OCH3 or CH3CH2CH2CH2OH 
Which of the following pure compounds will exhibit hydrogen bonding? (a) CH3CH2OH  (b) CH2O  (c) C2H4  (d) C2H2  (e) CH3OCH3  (f ) CH3NH2  (g) C3H8  (h) NH3 
From the multiple options listed below (A through X), select the letter that correctly ranks the following compounds in order of decreasing boiling point.
There are two different compounds with molecular formula C2H6O. One of these isomers has a much higher boiling point than the other. Explain why. 
Consider the three compounds shown below and then answer the questions that follow:  (h) Which compound do you predict will have the highest boiling point? Explain. 
In each pair of molecules below, select the one with the greater predicted boiling point. 
Epichlorohydrin (1) is an epoxide used in the production of plastic, epoxy glues, and resins (reactions of epoxides will be discussed in Chapter 14). When epichlorohydrin is treated with phenol (2), two products are formed (3 and 4). At room temperature, these liquid products are difficult to separate from each other, but upon heating, these compounds are easily separated from one another. Explain these observations (Tetrahedron 2006, 62, 10968–10979). 
Select the molecule with the highest boiling point. Octane (CH3(CH2)6CH3) or Decane (CH3(CH2)8CH3)
Select the molecule with the highest boiling point. Acetone (CH3COCH3) or Propanoic acid (CH3CH2COOH)
The following compound is an amino acid derivative (Chapter 25). In solution, molecules of this compound show a tendency to “stick” together, or self-assemble, via a series of intermolecular hydrogen bonds. During self-assembly, the growing aggregate can entrap molecules of liquid, thereby forming a gel (J. Am. Chem. Soc. 2009, 131, 11478–11484).  (b) Draw the intermolecular hydrogen bonds that form during self- assembly. Do this by drawing three molecules stacked directly on top of each other, each in the orientation shown. Then, draw hydrogen bonds from the central molecule to each of the other two molecules, showing eight intermolecular H bonds between amide H’s on one molecule to amide O’s on adjacent molecules 
For each of the following, choose the best answer; give the letter. (a) Which has the lower heat of combustion: (i) (E)-3-hexene or (ii) 1-hexene?   (b) Which one has the higher heat of combustion: (i) (E)-cyclooctene or (ii) (Z)-cyclooctene?   (c) Which one has the lower boiling point: (i) chloroform or (ii) methylene chloride?   (d) Which one has the higher boiling point: (i) 1,1,1-trifluoroethane or (ii) hexafluoroethane?   (e) Which one is more dense: (i) 1-iodooctane or (ii) 1-bromooctane?   (f) Which one is more dense: (i) water or (ii) 1-iodooctane?   (g) Which one is thermodynamically more stable: (i) 3-methylcyclohexyl cation or (ii) 1-methylcyclohexyl cation?   (h) Which one can be the units of a first-order rate constant: (i) L mol−1 s−1 or (ii) s−1 ?    
Hydrogen fluoride has a dipole moment of 1.83 D; its boiling point is 19.34°C. Ethyl fluoride (CH3CH2F) has an almost identical dipole moment and has a larger molecular weight, yet its boiling point is -37.7°C. Explain.
Why does one expect the cis isomer of an alkene to have a higher boiling point than the trans isomer?
Molecule below shows hydrogen bonding on positions A-E. Indicated hydrogen bonding is correct in:a)    A, B, C and Db)    A, C, D and Ec)    A, B, D and Ed)    They all show correct hydrogen bonding 
              
Rank the following compounds in order from lowest boiling point to highest boiling point. 
The following compound is an amino acid derivative (Chapter 25). In solution, molecules of this compound show a tendency to “stick” together, or self-assemble, via a series of intermolecular hydrogen bonds. During self-assembly, the growing aggregate can entrap molecules of liquid, thereby forming a gel (J. Am. Chem. Soc. 2009, 131, 11478–11484). (a) Each of the six hydrogen atoms bound directly to nitrogen can form a hydrogen bond, but H’s that are on the amides can form stronger hydrogen bonds than H’s on the amines. Explain why this is so using resonance.
Rank following compounds by their expected  boiling point.
Circle the structure that shows appropriate  hydrogen bonding:
Using dashed line (-----) for each of the following indicate clearly on the picture below (label partial and full charges where necessary):a) hydrogen bondingb) dipole-dipolec) ion-dipole interaction 
Which compound has the lowest boiling point:  (a) CH3CH2CH2CH2CH2CH3 (b) (CH3)2CHCH2CH2CH3 (c) (CH3)3CCH2CH3
What are the strongest intermolecular forces in 1) hexane2) methanol 3) acetone4) 2-propanol5) water?The choices are: a) H-bondingb) dipole-dipolec) London dispersion.Please explain your answer.
The following compounds have similar molecular weights. Which has the highest boiling point.A)        CH3CH=OB)        C2H5OHC)        CH3OCH3D)        CH3CH2CH3
Rank these compounds by boiling point. pentane; neopentane; isopentane
Indicate what intermolecular forces occur in the following compound. (Select all that apply.) (a) van der Waals(b) dipole-dipole (c) hydrogen bonding (d) ion-ion
What type(s) of intermolecular forces are expected between CH3NH2 molecules? Indicate with a Y (yes) or an N (no) which apply.dipole forcesinduced dipole forceshydrogen bonding
Which of the molecules below has the LOWEST boiling point?
If a solid line represents a covalent bond and a dotted line represents intermolecular attraction, which of these choices shows a hydrogen bond? Check all that apply.
Rank the substances below from highest boiling point to lowest boiling point. 
Rank the following compounds in order of their boiling point, with the highest boiling point having the highest number and the lowest boiling point having the number 1.
Rank the substances below from highest boiling point to lowest boiling point
Which has the highest surface tension at room temperature?a. CH4b. Cl4c. CCl4d. CF4e. CBr4 
Which compound has the lowest boiling point? 
If a solid line represents a covalent bond and a dotted line represents intermolecular attraction, which of these choices a hydrogen bond? Check all that apply. 
Rank the following compounds according to their boiling point.  
Rank the following compounds accordign to their boiling point.  
Rank the following compounds from lowest to highest boiling point: 
What kind of nonbonding interaction occurs in liquids of the molecule shown in the figure (Figure 2)? (a) induced dipole (b) hydrogen bond (c) permanent dipole
Identify the intermolecular forces present in each compound. Select all that apply
What kind of nonbonding interaction occurs in liquids of the molecule shown in the figure (Figure 1)? (a) induced dipole (b) permanent dipole (c) hydrogen bond
What is the order of increasing boiling points in the following compounds?
Which of the following molecules is expected to have highest boiling point? a. Ib. IIc. IIId. IV
Ketones have a higher boiling point than alkanes or ethers because ofa. resonanceb. hydrogen bondingc. dipole-dipole interactionsd. ionic interactions 
Which of the following compounds has the highest bolling point? 
Which of the following compounds would have the highest boiling point?a. CH3CH3b. CH3OHc. CH3CH2CH2CH2CH3d. CH3CH2CH2CH2OH 
Predict which of the following compounds will have a lower bolling point than 1-butanal.Select one: a. 2-butanol b. 1-butene c. 1-butanol d. butanoic acid 
The compounds n-butane, CH3(CH2)2CH3 and trimethylamine, N(CH3)3 have very similar molecular weights. However, their melting points are appreciably different. Select the compound with the lowest melting point, and the correct reason why.a. trimethylamine, because it will experience dipolar forces between molecules b. n-butane, because it is unbranched c. trimethylamine, because it is more highly O branched than n-butane d. n-butane, because it will only experience dispersion forces between molecules