Recipes for Growing Sugar Crystals

Since I issued this website I got several requests for recipes to grow crystals, some asked especially for recipes to grow sugar crystals. It seems that the common recipes are only vague or not working sufficiently. One of the big problems growing crystals of sugar is its extreme high solubility and the high viscosity of its solution. The good thing is its available anywhere, its cheap and its not poisonous. If we talk about sugar we mean cane sugar as there are many kinds of different "sugars" which are all separate "chemicals" like glucose, fructose, xylose, maltose etc. Before we begin, something about units. Many of you may still be used to ounces, pounds, Fahrenheit etc. In spite the fact that I still use this units in this script sometimes I recommend strongly that you get used to metric units, its so much easier to calculate with them! If you buy scales, measuring caps etc. make sure that they have metric units, too. That makes it easier to switch.

Physical and Crystallographical Properties

chemical names : sucrose, saccharose, beta-D-Fructofuranosyl-alpha-D-glucopyranoside : C12H22O11 formula

molar mass Specific gravity melting point crystal class

: 342.30 : 1.587 : 160 - 186 C (under decomposition !) : monoclinic spenoidal

Either known as cane sugar when made out of sugar cane or as beet sugar when made out of sugar beets. Dont be confused both are the absolute identical chemical compound. Sugar is one of the purest commercially distributed organic "chemicals" produced in millions of tons. There is no need to buy analytical grade sugar for crystal growing experiments, its only something for scientists or if you have too much money. Just take the regular sugar from the next supermarket - watch for sales (sugar cannot rot)!

Sugar crystal floating in a saturated solution. Crystal size app. 10 mm, picture taken in polarized light

Crystal form of sugar How to grow sugar crystals from a solution in water
There are two simple basic methods to grow crystals from a solution

The Evaporation Method The Slowly Cooling Method

Using the evaporation method you simply let evaporate the solvent (e.g. water) of your saturated solution to get crystals. Its quite simple but may take a long time. If the solubility is low you may have to wait a very long time to get nicely sized crystals. Fortunately in the case of sugar the solubility is very high. Using the slowly cooling method you produce a hot saturated solution and let cool it down slowly to get the crystals. The catch is let it cool down slowly. As slower a solution cools down as bigger and finer the crystals will be. The second catch it does not work with substances which do not change solubility greatly with rising temperature (like regular table salt) or which solubility go down with rising temperatures.(this is not very common but it happens). Fortunately the solubility of sugar rises greatly when the temperature goes up.

The good thing is this method is quick you will get nice sized crystals within several hours to days.

The Evaporation Method

Dissolve per 100 gms of water 230 gms of sugar heat up the solution until it boils and gets clear. Then if you want filter use a regular coffee filter with paper, but filtering is not absolutely necessary. The solution may have a slight yellow hue. For heating up the solution use a cooking pot or a vessel made from heat resistant glass (Pyrex), as for example replacement jars for electric coffee machines. You may also use the microwave but of course only use vessels which are suitable for this (no metal or metal parts!). To grow the crystals you can use any kind of glass or plastic container with a wide open mouth. For example preservation glasses etc. You should produce at least about 500 ml of solution better around 1000 ml (or a quart). For a method how to calculate a specific volume of growing solution see the "Calculating a Solution" part down below. After the covered solution has cooled down then after two or three days there should be some sugar crystals at the bottom of the jar. If not, throw in some little grains of sugar. Let the solution stay alone and covered for about a week. If you got no crystals on the bottom, yet even after throwing in some sugar grains your solution can not be saturated and wont work. This may happen either because you made a mistake with the amounts of water and sugar used, or your room temperature is well above 20 C (app. 70 F). To avoid mistakes in the amounts of water and sugar used, use an electronic kitchen scale which should have at least a resolution of 2 gm. (better 1 gm.) most can be switched from oz./lbs. to metric, metric is easier to calculate. Also weigh the water, as its much more accurate than measuring the volume. If your room temperature is well above 20 C you have to adjust the initial recipe. If you look at the solubility table down below the solubility of sugar at 20 C is 203 gm. per 100 gm. of water. In the recipe we took 230 gm. (27 gm. added as security gap). If you work for example at a room temperature of 30 C you adjust the recipe to 250 gm. per 100 gm. of water (again app. 30 gm. as security gap). Okay everything worked fine, there are some crystals at the bottom and the solution rested for a week. Now pour the solution in your final freshly cleaned growing vessel. You may filter it but its not absolutely necessary and filtering the viscose solution may take forever. Now you need a seed crystal, usually you will find at the bottom nicely sized sugar crystals already suitable for this purpose or you may use a bought candy sugar crystal (thats cheating !). Dry up the crystal with some paper towel and fix it with a slip knot to a thread of "invisible sewing thread" which is a thin clear thread of nylon or use very thin fishing line. Dont use regular threads made out of cotton etc. as they work like a wick and are easily visible in the ready crystal. Fix the thread to a piece of wood or a pencil for example so that the crystal suspends somehow above 2 - 3 cm (about one inch) the bottom of your growing vessel but well below the surface of the solution. Before doing that rinse the crystal on the thread shortly in cold water. The growing vessel must stay open to allow the water to evaporate but you may cover it with a thin paper towel (most paper towels are multi-layer so you may split them) to

prevent flies, wasps, dust etc. from falling into the solution. As the water evaporates your seed crystal will grow. This will not work if you are in a very humid climate or if your room temperature changes and goes up. As evaporation goes on there may grow additional crystals on the bottom of the vessel on the thread or on the sides. They grow on the cost of your desired main crystal. If so, pour the solution in a freshly cleaned other vessel rinse the crystal and the thread shortly in cold water (remove additional crystals which may have formed on the thread) and go on with evaporation.

Fixing a seed crystal to a thread with a slipknot

There is not enough solution in this growing vessel

Additional crystals at the bottom grow on the cost of your main crystal !

The Slowly Cooling Method

If you produced the saturated solution for the evaporation method and found some crystals at the bottom you already used the slowly cooling method to produce crystals! To get bigger and better ones you just have to add more sugar (larger "security gap") and take care that the solution cools down very slowly. A good basic recipe is to add 230 to 300 gm. of sugar to 100 gm. of water and to heat it up until the solution boils and gets clear. You may filter it if you want but its not absolutely necessary. Pour the solution in your final growing vessel and close it tightly. Take care that the solution cools down very slowly by insulating it and also avoid any moving, shaking or vibration of the solution. You may give the crystals a better surface to grow, a matrix, if you put in a piece of rock, or have it suspended on a thread, or use a metal paper clip on a thread. It takes a few hours to days, depending on how much solution you take and how good your insulation is, until the solution has cooled down to room temperature and the crystals are

ready. They main problems you may have with the slowly cooling method is that the solution does not cool down slowly enough, which results in small crystals or your solution has cooled down but there are no crystals at all! What happened? Super saturation! Your solution contains much more sugar than "allowed" since there have not been formed any seed crystals spontaneously. If the solution is disturbed or you throw in some little sugar grains crystallization starts immediately. Since the growing velocity of sugar crystals is small, solutions are often slightly supersaturated when they have cooled down and so the crystals still grow a little while even if the temperature does not change anymore. So allow the crystals some extra time.

The Trick with the Thermal Ballast

As more volume of solution you have as longer it will take to cool down. The reason is that the surface of your vessel is growing by power of two but your volume and so the amount of heat energy is growing by power of three if you enlarge the dimension of your vessel. The heat loss depends on the surface area available. To give you a simple example lets say we have a cubic container of 1 inch, so the surface is 6 square inches and the volume one cubic inch. Now lets take a container of 10 inches size the volume will be 10*10*10 = 1000 cubic inches but the surface only 6*10*10 = 600 inches. With the small container you have a volume/surface ratio of 1 to 6 with the big one a ratio of 10 to 6 and its a good guess that cooling down takes ten times longer. So that was the physical principle! However, who wants to handle gigantic amounts of solution just to grow some little crystals? Nobody told you that all of the volume must be solution! Only a small amount of solution and a large amount of water will have the same effect if you keep them separated. The pictures down below explain that to you. Just heat up a big cooking pot of water and separately prepare some solution. Then put the container with the hot solution in your cooking pot with hot boiling water. Take care that both are tightly closed. If you put your cooking pot in a big box with insulation material, like Styrofoam, cotton, rock wool, saw dust etc. you get a real slow cooling down of several days up to over a week. If you use an electronic thermometer you can watch the temperature falling.

Heating up the thermal ballast and your solution separately

Now the crystals grow in your "cooking box".

Calculating a Solution
You often will have the problem that you need a specific volume of solution to fill a growing vessel efficiently. Lets take for example you want to use the slowly cooling method, have a 1000 ml jar and you want to have about 800 ml of solution which contains 260 gm. of sugar per 100 gm. of water. The specific gravity of sugar is 1.587, so 260 gm. have a volume of 260/1.587 = 163.8 ml + the 100 gm. of water (which are almost exactly 100 ml) you get a volume of 263.8 ml. To fill up 800 ml you need 800/263.8= 3.03 times your basic recipe. That is 3.03*100 gm. = 303 gm. of water and 3.03*260 gm. = 787.8 gm. of sugar. If you take 300 gm. of water and 790 gm. of sugar you will also be fine. If you do not want to calculate by hand you can use this little calculator.

Conclusion
Following these instruction you did not only learn something about growing sugar crystals but the basics of solution growth anyhow. The principles are the same growing other materials and there are more recipes to come. Please be patient and give me some time. If you have questions or comments or you got nice results please eMail me (pics are welcome).

Solubility table for sugar in water

In gm. of sugar per 100 gm. of water and ounces of sugar per pound of water
T in C 0 oz./lb 5 10 15 20 25 30 35 40 45 50

g/100 g 179.2 184.8 190.6 196.9 203.8 211.3 219.4 228.4 238.1 248.8 260.5 28.67 29.56 30.50 31.51 32.61 33.80 35.11 36.54 38.10 39.81 41.68

T in C 55 oz./lb

60

65

70

75

80

85

90

95

100

g/100 g 273.3 287.4 303.0 320.4 339.9 362.0 387.1 415.8 448.9 487.2 43.72 45.98 48.48 51.26 54.39 57.92 61.94 66.54 71.83 77.94

And here the same thing in degrees Fahrenheit!

T in F 35 40 45 50 55 60 65 70 75 80 85 90

g/100 g 181.0 184.1 187.3 190.6 194.1 197.7 201.4 205.4 209.5 213.9 218.5 223.3 oz./lbs 28.96 29.46 29.97 30.50 31.05 31.63 32.23 32.86 33.53 34.23 34.96 35.73

T in F 95

100

105

110

115

120

125

130

135

140

145

150

g/100 g 228.4 233.7 239.3 245.1 251.3 257.8 264.6 271.8 279.4 287.4 295.9 304.8 oz./lbs 36.54 37.39 38.28 39.22 40.21 41.25 42.34 43.49 44.70 45.98 47.34 48.77

T in F 155

160

165

170

175

180

185

190

195

200

205

210

g/100 g 314.4 324.5 335.4 347.0 359.4 372.7 387.1 402.6 419.3 437.4 456.9 478.2 oz./lbs 50.30 51.93 53.66 55.52 57.50 59.64 61.94 64.41 67.09 69.98 73.11 76.51

Solubility chart of sugar

What is sugar? The white stuff we know as sugar is sucrose, a molecule composed of 12 atoms of carbon, 22 atoms of hydrogen, and 11 atoms of oxygen (C12H22O11). Like all compounds made from these three elements, sugar is a carbohydrate. Its found naturally in most plants, but especially in sugarcane and sugar beets hence their names. Sucrose is actually two simpler sugars stuck together: fructose and glucose. In recipes, a little bit of acid (for example, some lemon juice or cream of tartar) will cause sucrose to break down into these two components. If you look closely at dry sugar, youll notice it comes in little cubelike shapes. These are sugar crystals, orderly arrangements of sucrose molecules. What happens when you heat a sugar solution? When you add sugar to water, the sugar crystals dissolve and the sugar goes into solution. But you cant dissolve an infinite amount of sugar into a fixed volume of water. When as much sugar has been dissolved into a solution as possible, the solution is said to be saturated. The saturation point is different at different temperatures. The higher the temperature, the more sugar that can be held in solution. When you cook up a batch of candy, you cook sugar, water, and various other ingredients to extremely high temperatures. At these high temperatures, the sugar remains in solution, even though much of the water has boiled away. But when the candy is through cooking and begins to cool, there is more sugar in solution than is normally possible. The solution is said to be supersaturated with sugar. Supersaturation is an unstable state. The sugar molecules will begin to crystallize back into a solid at the least provocation. Stirring or jostling of any kind can cause the sugar to begin crystallizing. Why are crystals undesirable in some candy recipesand how do you stop them from forming?
Under a microscope, you can see that sugar crystals arent cubes, exactly, but oblong and slanted at both ends. (Image courtesy of Nutrition and Food Management Dept., Oregon State University)

The fact that sugar solidifies into crystals is extremely important in candy making. There are basically two categories of candies - crystalline (candies which contain crystals in their finished form, such as fudge and fondant), and noncrystalline, or amorphous (candies which do not contain crystals, such as lollipops, taffy, and caramels). Recipe ingredients and procedures for noncrystalline candies are specifically designed to prevent the formation of sugar crystals, because they give the resulting candy a grainy texture.

One way to prevent the crystallization of sucrose in candy is to make sure that there are other types of sugarusually, fructose and glucoseto get in the way. Large crystals of sucrose have a harder time forming when molecules of fructose and glucose are around. Crystals form something like Legos locking together, except that instead of Lego pieces, there are molecules. If some of the molecules are a different size and shape, they wont fit together, and a crystal doesnt form. A simple way to get other types of sugar into the mix is to "invert" the sucrose (the basic white sugar you know well) by adding an acid to the recipe. Acids such as lemon juice or cream of tartar, cause sucrose to break up (or invert) into its two simpler components, fructose and glucose. Another way is to add a nonsucrose sugar, such as corn syrup, which is mainly glucose. Some lollipop recipes use as much as 50% corn syrup; this is to prevent sugar crystals from ruining the texture. Fats in candy serve a similar purpose. Fatty ingredients such as butter help interfere with crystallizationagain, by getting in the way of the sucrose molecules that are trying to lock together into crystals. Toffee owes its smooth texture and easy breakability to an absence of sugar crystals, thanks to a large amount of butter in the mix.

Interfering agents (Image courtesy of Nutrition and Food Management Dept., Oregon State University)

How to calculate Sugar saturation point?

Relevant answers:

What is the saturation point of sugar in water? Water at 25C will be saturated with sugar at a ratio of 100 grams of sugar to 100 grams of water.

What does saturation point have to do with dew point? The dew pt. is the temperature @ which the air would become saturated if you cooled it. Read more: http://wiki.answers.com/Q/What_does_saturation_point_have_to_do_with_dew_poi nt#ixzz1XOxjgHau

What is the saturation point of sugar in water at room temperature and at water's boiling point? The saturation point of sugar in room temperature is a 2 to 1 ratio and for the saturation point of sugar in boiling water is a 1 to 1 ratio! Hope this helps :( !!!!!

What is the saturation point of salt? It rises a little bit with temperature (warmer water, more salt can be added), but is basically about 26-28%. Here is a nice chart: http://en.wikipedia.org/wiki/File:SolubilityVsTemperature.png So,...

Read more: http://wiki.answers.com/Q/How_to_calculate_Sugar_saturation_point#ixzz1XOxUaRA7

Water activity
Water activity or aw was developed to account for the intensity with which water associates with various non-aqueous constituents and solids. Simply stated, it is a measure of the energy status of the water in a system. It is defined as the vapor pressure of a liquid divided by that of pure water at the same temperature; therefore, pure distilled water has a water activity of exactly one. As the temperature increases, aw typically increases, except in some products with crystalline salt or sugar. Higher aw substances tend to support more microorganisms. Bacteria usually require at least 0.91, and fungi at least 0.7. See fermentation. Water migrates from areas of high aw to areas of low aw. For example, if honey (aw 0.6) is exposed to humid air (aw 0.7) the honey will absorb water from the air.

Formulae
Definition of aw:

where p is the vapor pressure of water in the substance, and p is the vapor pressure of pure water at the same temperature. Alternate definition:

where lw is the activity coefficient of water and xw is the mole fraction of water in the aqueous fraction. Relative humidity: The relative humidity of air in equilibrium with a sample is called the Equilibrium Relative Humidity (ERH).[1]

Estimated mold-free shelf life in days at 21 C:

[citation needed]

Uses for water activity

Water activity is an important consideration for food product design and food safety.

Food product design

Food designers use water activity to formulate products that are shelf stable. If a product is kept below a certain water activity, then mold growth is inhibited. This results in a longer shelf-life. Water activity values can also help limit moisture migration within a food product made with different ingredients. If raisins of a higher water activity are packaged with bran flakes of a lower water activity, the water from the raisins will migrate to the bran flakes over time, resulting in hard raisins and soggy bran flakes. Food formulators use water activity to predict how much moisture migration will affect their product.

Food safety
Water activity is used in many cases as a critical control point for Hazard Analysis and Critical Control Points (HACCP) programs. Samples of the food product are periodically taken from the production area and tested to ensure water activity values are within a specified range for food quality and safety. Measurements can be made in as little as five minutes, and are made regularly in most major food production facilities. For many years, researchers tried to equate bacterial growth potential with moisture content. They found that the values were not universal, but specific to each food product. W J Scott in 1953 first established that it was water activity, not water content that correlated with bacterial growth. It is firmly established that growth of bacteria is inhibited at specific water activity values. U.S. Food and Drug Administration (FDA) regulations for intermediate moisture foods are based on these values.

Lowering the water activity of a food product should not be seen as a kill step. Studies in powdered milk show that viable cells can exist at much lower water activity values, but that they will never grow. Over time, bacterial levels will decline.

Water activity measurement

Water activity values are obtained by either a capacitance or a dew point hygrometer.

Capacitance hygrometers
Capacitance hygrometers consist of two charged plates separated by a polymer membrane dielectric. As the membrane adsorbs water, its ability to hold a charge increases and the capacitance is measured. This value is roughly proportional to the water activity as determined by a sensor-specific calibration. Capacitance hygrometers are not affected by most volatile chemicals and can be much smaller than other alternative sensors. They do not require cleaning, but are less accurate than dew point hygrometers (+/- .015 aw). They should have regular calibration checks and can be affected by residual water in the polymer membrane (hysteresis).

Dew point hygrometers

Red line shows saturation

The temperature at which dew forms on a clean surface is directly related to the vapor pressure of the air. Dew point hygrometers work by placing a mirror over a closed sample chamber. The mirror is cooled until the dew point temperature is measured by means of an optical sensor. This temperature is then used to find the relative humidity of the chamber using psychrometric charts. This method is theoretically the most accurate (+/- .003 aw) and often the fastest. The sensor requires cleaning if debris accumulates on the mirror.

Equilibration
With either method, vapor equilibrium must occur in the sample chamber. This will take place over time or can be aided by the addition of a fan in the chamber. Thermal equilibrium must also take place unless the sample temperature is measured.

Water activity and moisture content

Water activity is related to moisture content in a non-linear relationship known as a moisture sorption isotherm curve. These isotherms are substance and temperature specific. Isotherms can be used to help predict product stability over time in different storage conditions.

Use in humidity control

There is net evaporation from a solution with a water activity greater than the relative humidity of its surroundings. There is net absorption of water by a solution with a water activity less than the relative humidity of its surroundings. Therefore, in an enclosed space, a solution can be used to regulate humidity. [2]

Selected aw values
Example foods
Substance aw [3] Distilled Water 1 Tap water 0.99 Raw meats 0.99[3] Milk 0.97 Juice 0.97 Salami .87[3] Cooked bacon < 0.85 Saturated NaCl solution 0.75 Point at which cereal loses crunch 0.65

Dried fruits Typical indoor air Honey Dried fruit

0.60[3] 0.5 - 0.7 0.5 - 0.7 0.5 - 0.6

aw values of microorganism inhibition

Microorganism Inhibited aw Clostridium botulinum A, B .97 Clostridium botulinum E .97 Pseudomonas fluorescens .97 Clostridium perfringens .95 Escherichia coli .95 Salmonella .95 Vibrio cholerae .95 Bacillus cereus .93 Listeria monocytogenes .92 Bacillus subtilis .91 Staphylococcus aureus .86[4] Most molds .80[4] No microbial proliferation .50 Water activity is defined as the water requirements for survival or growth of microorganisms. But water activity is not the same as the amount of water in a product. In some cases, the water is bound to other molecules (say, Epsom salts) and isn't free for usage by the microbes. In other cases, the water is bound by humectants like sorbitol or glycerin (anywhere from 10% to 20% will bind water). So water activity is actually a measure of the amount of free (unbound or active) water molecules present in our products. Water activity increases or decreases with with increases or decreases in pressure and temperature. pH also plays a role. When we dissolve a solute like salt or sugar into water, the amount of water available to our beasties decreases so we say the water activity is reduced. Reduce it enough, and you've got an environment inhospitable to microbes. If the microbes don't have enough water, they die or go into a dormant state. (Remember the post the other day on osmosis? This is how salt or sugar kills them!) So, it looks like that not using a preservative in your sugar or salt scrub will work with two disclaimers... Disclaimer one: There are some microbes that can live in really hostile environments - like the xerophilic fungus (0.61 to 0.99) or the osmophilic yeasts (0.65 to 0.81) - and there are some, mostly yeasts, that will go into a dormant state waiting for water to come their way

and bring them back to life. Add a little unbound water to the mix (let's say you have wet hands and leave a puddle in the top of the product), and you've got yourself a fungal party! Disclaimer two: How do we figure out how much water is bound in our products and how much isn't? There's a lengthy formula that takes into account the water in the product, the partial pressure of the water vapour above the surface of the product, the relative humidity, and temperature, and by figuring all of that out, we can figure out the water activity of the product at that moment. If I take a look my sugar scrubs, I use about 140% sugar to 100% oils, which means I'm well above the numbers for killing bacteria and yeast. So should I use a preservative in my salt or sugar scrub? I'm still firmly on the side of "yes", because I'm always worried about what the end user will do with the product, but there is some evidence here that you could use lower levels of preservatives or possibly none. (Please do not take this that I am endorsing not using preservatives in scrubs!) Thanks for the question, research, and work you put into your comment, p! It's definitely food for thought!

Sucrose. Sucrose has the greatest solubility of the disaccharid sugars. Browne in his "Handbook of Sugar Analysis" states that, at 20C, 204 grams are soluble in 100 cc. of water. Thus at room temperature about 2 grams of sucrose are soluble in 1 cc. of water. At 100C 487 grams of sucrose are soluble in 100 cc. of water. For solubilities at other temperatures see Table 5. In Table 5 the solubility of sucrose is expressed in two ways. In column 2 is given the amount of sucrose dissolved in water to make 100 grams of solution. Thus at 0C, 64.18 grams of sucrose are dissolved in 35.82 grams of water to give a total of 100 grams of solution. The third column states the number of grams of sucrose dissolved in 100 grams of water at a definite temperature. Table 5 Solubility of Sucrose in Water at Different Temperatures Temperature, degrees C. 0 5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80 85 90 95 100 Grams of sucrose in 100 grams of solution, or per cent 64.18 64.87 65.58 66.30 67.09 67.89 68.70 69.55 70.42 71.32 72.25 73.20 74.18 75.18 76.22 77.27 78.36 79.46 80.61 81.77 82.87 Grams of sucrose Specific gravity dissolved by 100 grams of of solution water 179.2 184.7 190.5 197.0 203.9 211.4 219.5 228.4 238.1 248.7 260.4 273.1 287.3 302.9 320.5 339.9 362.1 386.8 415.7 448.6 487.2 1.31490 1.31920 1.32353 1.32804 1.33272 1.33768 1.34273 1.34805 1.35353 1.35923 1.36515 1.37124 1.37755 1.38404 1.39083 1.39772 1.40493 1.41225 1.41996 1.42778 1.43594

Percentage of Sucrose in Saturated Solutions. From Table 5 the percentage of sugar may be obtained. At 0C, 64.18 grams of sugar and 35.82 grams of water give 100 grams of solution, so that the number of grams of sugar may be read as percentage of sucrose or 64.18 per cent.
Solubility is a direct function of temperature. As temperature increases, solubility also increases and vice versa. Therefore, more sugar would dissolve in hot water than in cold water. That means that the saturation point in hotter water is higher than that in cooler water. When the temperature is decreased, the solubility of sugar in water decreases. But the water contains more sugar than this solubility because it was dissolved at a higher temperature. So, what happens here is that the amount of sugar above the saturation limit at this cooler temperature comes out of the solution. We see this as formation of sugar crystals in the water. Temperature and Solubility of Solids Increased temperature usually increases the solubility of solids in liquids. To understand why, we need to return to the Second Law of Thermodynamics. Increased temperature means a greater average velocity for the particles. This allows them to move from one position to another more easily. The greater freedom of movement allows the system to change its state more easily, and in keeping with the Second Law, it changes to the most probable state available, that is, the most dispersed state of which it is capable. Solids are very condensed systems, so the dissolving of a solid usually leads to a more dispersed system. Therefore, although there are exceptions, an increase in temperature generally leads to an increase in a solids solubility. The table below shows the change in solubility with changing temperature for glucose in water. Solubility of Glucose Solubility in grams of glucose per 100 mL of water 91 125 244 357 556

Temperature 25 C 30 C 50 C 70 C 90 C

The change in solubility with change in temperature can be used to create solutions with more solute dissolved than is predicted by the solubility of the substance. For example, the solubility of glucose at 25 C is 91 g glucose per 100 mL of water, and the solubility of glucose at 50 C is 244 g glucose per 100 mL of water. Therefore, if we add 100 g of glucose to 100 mL water at 25 C, 91 g dissolve. Nine grams of solid remain on the bottom, and the solution is saturated at this temperature. If we then heat the mixture to 50 C, the remaining 9 grams of glucose will dissolve.

At the new temperature, the solubility limit in 100 mL of water is 244 g glucose. With only 100 g of glucose dissolved, our system is now unsaturated. If we now slowly cool the mixture back to 25 C, 9 g of glucose should precipitate from solution. Sometimes this happens immediately, but sometimes it takes a while for the glucose molecules to find their positions in a solid structure. In the time between the cooling of the solution and the formation of glucose crystals, the system has a higher amount of dissolved glucose (100 grams) than is predicted by the solubility limit at 25 C (91 grams). Because the solution contains more dissolved solute than is predicted by the solubility limit, we say the solution is supersaturated.

Rock candy is produced from a supersaturated solution of sugar. You can make it by adding more sugar to water than will dissolve at room temperature, heating the mixture until the solubility limit has been increased enough to allow all of the sugar to dissolve, suspending a string in the hot solution, and allowing the solution to cool slowly back to room temperature. The solution remains supersaturated for a long while. Sugar molecules, which are relatively large, are slow to find the proper positions for crystal formation. Meanwhile, collisions with water molecules keep knocking them apart. Eventually, however, solid begins to form on the protected, irregular surfaces of the suspended string. Dissolved sugar molecules collide with the solid precipitating onto the string and gradually create the large, well-formed sugar crystals that we call rock candy. Total Maximum Solubility With Cane Sugar And Invert Sugar

(Tarr and Baker) Temperature, C. 20 25 30 Grams of cane sugar per 100 grams solution 37.1 35.7 33.4 Grams of invert sugar per 100 grams solution 38.6 41.4 45.6 Grams of water per 100 grams solution 24.3 22.9 21.0

Tolman, Munson, and Bigelow in 1901 obtained results, which we are now able to interpret on the basis of our present knowledge, on the inversion of sucrose by juices of different fruits. Their work was published before hydrogen-ion concentration was thought of in connection with jelly making. After determining the amount of invert sugar in a series of jellies and jams that they had made, they concluded that the inversion of the sucrose varies with the total amount of free organic acid present and the length of time the product is heated. But they found some exceptions to their conclusions. Crab-apple jelly with 0.17 per cent acid (as sulfuric) gave an inversion of 58.8 per cent of the sucrose, whereas orange jelly of the same acidity gave only 4.9 per cent of sucrose inverted. Since the inversion is in proportion to the hydrogen-ion concentration if time of heating is constant, the greatest inversion occurred with the acid giving the highest hydrogen-ion concentration, the tartaric acid of the grape. In this instance the total acidity was higher too. Plum with a high total acidity of 1.35 per cent yielded a lower percentage inverted than the grape with a total acidity of 0.69 per cent. The plum contains malic acid, which would result in a lower hydrogen-ion concentration than the tartaric.

Why Do Some Solids Dissolve in Water? The sugar we use to sweeten coffee or tea is a molecular solid, in which the individual molecules are held together by relatively weak intermolecular forces. When sugar dissolves in water, the weak bonds between the individual sucrose molecules are broken, and these C12H22O11 molecules are released into solution.

It takes energy to break the bonds between the C12H22O11 molecules in sucrose. It also takes energy to break the hydrogen bonds in water that must be disrupted to insert one of these sucrose molecules into solution. Sugar dissolves in water because energy is given off when the slightly polar sucrose molecules form intermolecular bonds with the polar water molecules. The weak bonds that form between the solute and the solvent compensate for the energy needed to disrupt the structure of both the pure solute and the solvent. In the

case of sugar and water, this process works so well that up to 1800 grams of sucrose can dissolve in a liter of water. Ionic solids (or salts) contain positive and negative ions, which are held together by the strong force of attraction between particles with opposite charges. When one of these solids dissolves in water, the ions that form the solid are released into solution, where they become associated with the polar solvent molecules.

H2O NaCl(s) Na+(aq) + Cl-(aq)

We can generally assume that salts dissociate into their ions when they dissolve in water. Ionic compounds dissolve in water if the energy given off when the ions interact with water molecules compensates for the energy needed to break the ionic bonds in the solid and the energy required to separate the water molecules so that the ions can be inserted into solution.

Solubility Equilibria Discussions of solubility equilibria are based on the following assumption: When solids dissolve in water, they dissociate to give the elementary particles from which they are formed. Thus, molecular solids dissociate to give individual molecules H2O C12H22O11(s) C12H22O11(aq)

and ionic solids dissociate to give solutions of the positive and negative ions they contain. H2O NaCl(s) Na+(aq) + Cl-(aq)

When the salt is first added, it dissolves and dissociates rapidly. The conductivity of the solution therefore increases rapidly at first. dissolve NaCl(s) dissociate Na+(aq) + Cl-(aq)

The concentrations of these ions soon become large enough that the reverse reaction starts to compete with the forward reaction, which leads to a decrease in the rate at which Na+ and Cl- ions enter the solution. associate Na+(aq) + Cl-(aq) precipitate Eventually, the Na+ and Cl- ion concentrations become large enough that the rate at which precipitation occurs exactly balances the rate at which NaCl dissolves. Once that happens, there is no change in the concentration of these ions with time and the reaction is at equilibrium. When this system reaches equilibrium it is called a saturated solution, because it contains the maximum concentration of ions that can exist in equilibrium with the solid salt. The amount of salt that must be added to a given volume of solvent to form a saturated solution is called the solubility of the salt. NaCl(s)

Solubility Rules There are a number of patterns in the data obtained from measuring the solubility of different salts. These patterns form the basis for the rules outlined in the table below, which can guide predictions of whether a given salt will dissolve in water. These rules are based on the following definitions of the terms soluble, insoluble, and slightly soluble.

A salt is soluble if it dissolves in water to give a solution with a concentration of at least 0.1 moles per liter at room temperature. A salt is insoluble if the concentration of an aqueous solution is less than 0.001 M at room temperature. Slightly soluble salts give solutions that fall between these extremes.

Solubility Rules for Ionic Compounds in Water

Soluble Salts 1. The Na , K , and NH4 ions form soluble salts. Thus, NaCl, KNO3, (NH4)2SO4, Na2S, and (NH4)2CO3 are soluble. 2. The nitrate (NO3-) ion forms soluble salts. Thus, Cu(NO3)2 and Fe(NO3)3 are soluble. 3. The chloride (Cl-), bromide (Br-), and iodide (I-) ions generally form soluble salts. Exceptions to this rule include salts of the Pb2+, Hg22+, Ag+, and Cu+ ions. ZnCl2 is soluble, but CuBr is not. 4. The sulfate (SO42-) ion generally forms soluble salts. Exceptions include BaSO4, SrSO4, and PbSO4, which are insoluble, and Ag2SO4, CaSO4, and Hg2SO4, which are slightly soluble.
+ + +

Insoluble Salts 1. Sulfides (S ) are usually insoluble. Exceptions include Na2S, K2S, (NH4)2S, MgS, CaS, SrS, and BaS. 2. Oxides (O2-) are usually insoluble. Exceptions include Na2O, K2O, SrO, and BaO, which are soluble, and CaO, which is slightly soluble. 3. Hydroxides (OH-) are usually insoluble. Exceptions include NaOH, KOH, Sr(OH)2, and Ba(OH)2, which are soluble, and Ca(OH)2, which is slightly soluble. 4. Chromates (CrO42-) are usually insoluble. Exceptions include Na2CrO4, K2CrO4, (NH4)2CrO4, and MgCrO4. 5. Phosphates (PO43-) and carbonates (CO32-) are usually insoluble. Exceptions include salts of the Na+, K+, and NH4+ ions.
2-