Hygroscopy

The word hygroscopy (/haɪˈɡrɒskəpi/) uses combining forms of hygro- and -scopy. Unlike any other -scopy word, it no longer refers to a viewing or imaging mode. It did begin that way, with the word hygroscope referring in the 1790s to measuring devices for humidity level. These hygroscopes used materials, such as certain animal hairs, that appreciably changed shape and size when they became damp. Such materials were then said to be hygroscopic because they were suitable for making a hygroscope. Eventually, though, the word hygroscope ceased to be used for any such instrument in modern usage. But the word hygroscopic (tending to retain moisture) lived on, and thus also hygroscopy (the ability to do so). Nowadays an instrument for measuring humidity is called a hygrometer (hygro- + -meter).

Early hygroscopy literature began circa 1880.[1] Studies by Victor Jodin (Annales Agronomiques, October 1897) focused on the biological properties of hygroscopicity.[2] He noted pea seeds, both living and dead (without germinative capacity), responded similarly to atmospheric humidity, their weight increasing or decreasing in relation to hygrometric variation.

Marcellin Berthelot viewed hygroscopicity from the physical side, a physico-chemical process. Berthelot's principle of reversibility, briefly- that water dried from plant tissue could be restored hygroscopically, was published in "Recherches sur la desiccation des plantes et des tissues végétaux; conditions d'équilibre et de réversibilité," (Annales de Chimie et de Physique, April 1903).[2]

Léo Errera viewed hygroscopicity from perspectives of the physicist and the chemist.[2] His memoir "Sur l'Hygroscopicité comme cause de l'action physiologique à distance" (Recueil de l'lnstitut Botanique Léo Errera, Université de Bruxelles, tome vi., 1906) provided a hygroscopy definition that remains valid to this day. Hygroscopy is "exhibited in the most comprehensive sense, as displayed

(a) in the condensation of the water-vapour of the air on the cold surface of a glass;

(b) in the capillarity of hair, wool, cotton, wood shavings, etc.;

(c) in the imbibition of water from the air by gelatine;

(d) in the deliquescence of common salt;

(e) in the absorption of water from the air by concentrated sulphuric acid;

(f) in the behaviour of quicklime".[2]

Apparatus for the determination of the hygroscopicity of fertilizer, Fixed Nitrogen Research Laboratory, ca. 1930

Hygroscopic substances include cellulose fibers (such as cotton and paper), sugar, caramel, honey, glycerol, ethanol, wood, methanol, sulfuric acid, many fertilizer chemicals, many salts (like calcium chloride, bases like sodium hydroxide etc.), and a wide variety of other substances.[3]

If a compound dissolves in water, then it is considered to be hydrophilic.[4]

Zinc chloride and calcium chloride, as well as potassium hydroxide and sodium hydroxide (and many different salts), are so hygroscopic that they readily dissolve in the water they absorb: this property is called deliquescence. Not only is sulfuric acid hygroscopic in concentrated form but its solutions are hygroscopic down to concentrations of 10% v/v or below. A hygroscopic material will tend to become damp and cakey when exposed to moist air (such as the salt inside salt shakers during humid weather).

Because of their affinity for atmospheric moisture, desirable hygroscopic materials might require storage in sealed containers. Some hygroscopic materials, e.g., sea salt and sulfates, occur naturally in the atmosphere and serve as cloud seeds, cloud condensation nuclei (CCNs). Being hygroscopic, their microscopic particles provide an attractive surface for moisture vapour to condense and form droplets. Modern-day human cloud seeding efforts began in 1946.[5]

When added to foods or other materials for the express purpose of maintaining moisture content, hygroscopic materials are known as humectants.

Materials and compounds exhibit different hygroscopic properties, and this difference can lead to detrimental effects, such as stress concentration in composite materials. The volume of a particular material or compound is affected by ambient moisture and may be considered its coefficient of hygroscopic expansion (CHE) (also referred to as CME, or coefficient of moisture expansion) or the coefficient of hygroscopic contraction (CHC)—the difference between the two terms being a difference in sign convention.

Differences in hygroscopy can be observed in plastic-laminated paperback book covers—often, in a suddenly moist environment, the book cover will curl away from the rest of the book. The unlaminated side of the cover absorbs more moisture than the laminated side and increases in area, causing a stress that curls the cover toward the laminated side. This is similar to the function of a thermostat's bimetallic strip. Inexpensive dial-type hygrometers make use of this principle using a coiled strip. Deliquescence is the process by which a substance absorbs moisture from the atmosphere until it dissolves in the absorbed water and forms a solution. Deliquescence occurs when the vapour pressure of the solution that is formed is less than the partial pressure of water vapour in the air.

While some similar forces are at work here, it is different from capillary attraction, a process where glass or other solid substances attract water, but are not changed in the process (e.g., water molecules do not become suspended between the glass molecules).

Deliquescence, like hygroscopy, is also characterized by a strong affinity for water and tendency to absorb moisture from the atmosphere if exposed to it. Unlike hygroscopy, however, deliquescence involves absorbing sufficient water to form an aqueous solution. Most deliquescent materials are salts, including calcium chloride, magnesium chloride, zinc chloride, ferric chloride, carnallite, potassium carbonate, potassium phosphate, ferric ammonium citrate, ammonium nitrate, potassium hydroxide, and sodium hydroxide. Owing to their very high affinity for water, these substances are often used as desiccants, also an application for concentrated sulfuric and phosphoric acids. Some deliquescent compounds are used in the chemical industry to remove water produced by chemical reactions (see drying tube).[6]

The seeds of some grasses have hygroscopic extensions that bend with changes in humidity, enabling them to disperse over the ground. An example is Needle-and-Thread, Hesperostipa comata.[7] Each seed has an awn that twists several turns when the seed is released. Increased moisture causes it to untwist, and, upon drying, to twist again, thereby drilling the seed into the ground.

Hygroscopic qualities of various materials illustrated in graph form; relative humidity on the X-axis and moisture content on the Y-axis.

Hygroscopicity is a general term used to describe a material's ability to absorb moisture from the environment.[13] There is no standard quantitative definition of hygroscopicity, so generally the qualification of hygroscopic and non-hygroscopic is determined on a case-by-case basis. For example, pharmaceuticals that pick up more than 5% by mass, between 40 and 90% relative humidity at 25 °C, are described as hygroscopic, while materials that pick up less than 1%, under the same conditions are regarded as non-hygroscopic.[14]

The amount of moisture held by hygroscopic materials is usually proportional to the relative humidity. Tables containing this information can be found in many engineering handbooks and is also available from suppliers of various materials and chemicals.

Hygroscopy also plays an important role in the engineering of plastic materials. Some plastics, e. g. nylon, are hygroscopic while others are not.

Many engineering polymers are hygroscopic, including nylon, ABS, polycarbonate, cellulose, carboxymethyl cellulose, and poly(methyl methacrylate) (PMMA, plexiglas, perspex).

Other polymers, such as polyethylene and polystyrene, do not normally absorb much moisture, but are able to carry significant moisture on their surface when exposed to liquid water.[15]

Type-6 nylon (a polyamide) can absorb up to 9.5% of its weight in moisture.[16]

The use of different substances' hygroscopic properties in baking are often used to achieve differences in moisture content and, hence, crispiness. Different varieties of sugars are used in different quantities to produce a crunchy, crisp cookie (UK: biscuit) versus a soft, chewy cake. Sugars such as honey, brown sugar, and molasses are examples of sweeteners used to create more moist, chewy cakes.[17]

• Efflorescent
• Hydrophile
• Hydrophobe
• Critical relative humidity
• Equilibrium moisture content

Look up hygroscopy or hygroscopic in Wiktionary, the free dictionary.

• Video on the deliquescense of calcium chloride
• The movement of hygroscopic organic salts