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104-613: The American forces believed the villagers of Vinh Moc were supplying food and armaments to the North Vietnamese garrison on the island of Con Co which was in turn hindering the American bombers on their way to bomb Hanoi. The idea was to force the villagers of Vinh Moc to leave the area but as is typical in Vietnam there was nowhere else to go. The villagers initially dug the tunnels to move their village 10 metres underground but

208-455: A Mohs hardness of 2 to 4, dense limestone can have a crushing strength of up to 180 MPa . For comparison, concrete typically has a crushing strength of about 40 MPa. Although limestones show little variability in mineral composition, they show great diversity in texture. However, most limestone consists of sand-sized grains in a carbonate mud matrix. Because limestones are often of biological origin and are usually composed of sediment that

312-463: A bloom of cyanobacteria or microalgae . However, stable isotope ratios in modern carbonate mud appear to be inconsistent with either of these mechanisms, and abrasion of carbonate grains in high-energy environments has been put forward as a third possibility. Formation of limestone has likely been dominated by biological processes throughout the Phanerozoic , the last 540 million years of

416-434: A carbonate rock outcrop can be estimated in the field by etching the surface with dilute hydrochloric acid. This etches away the calcite and aragonite, leaving behind any silica or dolomite grains. The latter can be identified by their rhombohedral shape. Crystals of calcite, quartz , dolomite or barite may line small cavities ( vugs ) in the rock. Vugs are a form of secondary porosity, formed in existing limestone by

520-616: A central quartz grain or carbonate mineral fragment. These likely form by direct precipitation of calcium carbonate onto the ooid. Pisoliths are similar to ooids, but they are larger than 2 mm in diameter and tend to be more irregular in shape. Limestone composed mostly of ooids is called an oolite or sometimes an oolitic limestone . Ooids form in high-energy environments, such as the Bahama platform, and oolites typically show crossbedding and other features associated with deposition in strong currents. Oncoliths resemble ooids but show

624-449: A change in environment that increases the solubility of calcite. Dense, massive limestone is sometimes described as "marble". For example, the famous Portoro "marble" of Italy is actually a dense black limestone. True marble is produced by recrystallization of limestone during regional metamorphism that accompanies the mountain building process ( orogeny ). It is distinguished from dense limestone by its coarse crystalline texture and

728-949: A composition reflecting the organisms that produced them and the environment in which they were produced. Low-magnesium calcite skeletal grains are typical of articulate brachiopods , planktonic (free-floating) foraminifera, and coccoliths . High-magnesium calcite skeletal grains are typical of benthic (bottom-dwelling) foraminifera, echinoderms , and coralline algae . Aragonite skeletal grains are typical of molluscs , calcareous green algae , stromatoporoids , corals , and tube worms . The skeletal grains also reflect specific geological periods and environments. For example, coral grains are more common in high-energy environments (characterized by strong currents and turbulence) while bryozoan grains are more common in low-energy environments (characterized by quiet water). Ooids (sometimes called ooliths) are sand-sized grains (less than 2mm in diameter) consisting of one or more layers of calcite or aragonite around

832-412: A considerable fraction of the limestone bed. At depths greater than 1 km (0.62 miles), burial cementation completes the lithification process. Burial cementation does not produce stylolites. When overlying beds are eroded, bringing limestone closer to the surface, the final stage of diagenesis takes place. This produces secondary porosity as some of the cement is dissolved by rainwater infiltrating

936-483: A drop of dilute hydrochloric acid is dropped on it. Dolomite is also soft but reacts only feebly with dilute hydrochloric acid, and it usually weathers to a characteristic dull yellow-brown color due to the presence of ferrous iron. This is released and oxidized as the dolomite weathers. Impurities (such as clay , sand, organic remains, iron oxide , and other materials) will cause limestones to exhibit different colors, especially with weathered surfaces. The makeup of

1040-637: A few million years, as this is the most stable form of calcium carbonate. Ancient carbonate formations of the Precambrian and Paleozoic contain abundant dolomite, but limestone dominates the carbonate beds of the Mesozoic and Cenozoic . Modern dolomite is quite rare. There is evidence that, while the modern ocean favors precipitation of aragonite, the oceans of the Paleozoic and middle to late Cenozoic favored precipitation of calcite. This may indicate

1144-455: A few thousand years. As rainwater mixes with groundwater, aragonite and high-magnesium calcite are converted to low-calcium calcite. Cementing of thick carbonate deposits by rainwater may commence even before the retreat of the sea, as rainwater can infiltrate over 100 km (60 miles) into sediments beneath the continental shelf. As carbonate sediments are increasingly deeply buried under younger sediments, chemical and mechanical compaction of

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1248-421: A given compound may increase or decrease with temperature. The van 't Hoff equation relates the change of solubility equilibrium constant ( K sp ) to temperature change and to reaction enthalpy change. For most solids and liquids, their solubility increases with temperature because their dissolution reaction is endothermic (Δ H  > 0). In liquid water at high temperatures, (e.g. that approaching

1352-490: A high percentage of the mineral dolomite , CaMg(CO 3 ) 2 . Magnesian limestone is an obsolete and poorly-defined term used variously for dolomite, for limestone containing significant dolomite ( dolomitic limestone ), or for any other limestone containing a significant percentage of magnesium . Most limestone was formed in shallow marine environments, such as continental shelves or platforms , though smaller amounts were formed in many other environments. Much dolomite

1456-447: A large increase in solubility with temperature (Δ H  > 0). Some solutes (e.g. sodium chloride in water) exhibit solubility that is fairly independent of temperature (Δ H  ≈ 0). A few, such as calcium sulfate ( gypsum ) and cerium(III) sulfate , become less soluble in water as temperature increases (Δ H  < 0). This is also the case for calcium hydroxide ( portlandite ), whose solubility at 70 °C

1560-687: A less humid climate zone, and the height of the tunnels allows visitors to stand upright. 17°04′23″N 107°06′40″E  /  17.073°N 107.111°E  / 17.073; 107.111 Limestone Limestone ( calcium carbonate CaCO 3 ) is a type of carbonate sedimentary rock which is the main source of the material lime . It is composed mostly of the minerals calcite and aragonite , which are different crystal forms of CaCO 3 . Limestone forms when these minerals precipitate out of water containing dissolved calcium. This can take place through both biological and nonbiological processes, though biological processes, such as

1664-422: A lesser extent, solubility will depend on the ionic strength of solutions. The last two effects can be quantified using the equation for solubility equilibrium . For a solid that dissolves in a redox reaction, solubility is expected to depend on the potential (within the range of potentials under which the solid remains the thermodynamically stable phase). For example, solubility of gold in high-temperature water

1768-435: A limestone sample except in thin section and are less common in ancient limestones, possibly because compaction of carbonate sediments disrupts them. Limeclasts are fragments of existing limestone or partially lithified carbonate sediments. Intraclasts are limeclasts that originate close to where they are deposited in limestone, while extraclasts come from outside the depositional area. Intraclasts include grapestone , which

1872-505: A long time to establish (hours, days, months, or many years; depending on the nature of the solute and other factors). The rate of dissolution can be often expressed by the Noyes–Whitney equation or the Nernst and Brunner equation of the form: where: For dissolution limited by diffusion (or mass transfer if mixing is present), C s {\displaystyle C_{s}}

1976-471: A lower Mg/Ca ratio in the ocean water of those times. This magnesium depletion may be a consequence of more rapid sea floor spreading , which removes magnesium from ocean water. The modern ocean and the ocean of the Mesozoic have been described as "aragonite seas". Most limestone was formed in shallow marine environments, such as continental shelves or platforms . Such environments form only about 5% of

2080-525: A lower diversity of organisms and a greater fraction of silica and clay minerals characteristic of marls . The Green River Formation is an example of a prominent freshwater sedimentary formation containing numerous limestone beds. Freshwater limestone is typically micritic. Fossils of charophyte (stonewort), a form of freshwater green algae, are characteristic of these environments, where the charophytes produce and trap carbonates. Limestones may also form in evaporite depositional environments . Calcite

2184-523: A mechanism for dolomitization, with one 2004 review paper describing it bluntly as "a myth". Ordinary seawater is capable of converting calcite to dolomite, if the seawater is regularly flushed through the rock, as by the ebb and flow of tides (tidal pumping). Once dolomitization begins, it proceeds rapidly, so that there is very little carbonate rock containing mixed calcite and dolomite. Carbonate rock tends to be either almost all calcite/aragonite or almost all dolomite. About 20% to 25% of sedimentary rock

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2288-411: A minimum, which is below 120 °C for most permanent gases ), but more soluble in organic solvents (endothermic dissolution reaction related to their solvation). The chart shows solubility curves for some typical solid inorganic salts in liquid water (temperature is in degrees Celsius , i.e. kelvins minus 273.15). Many salts behave like barium nitrate and disodium hydrogen arsenate , and show

2392-521: A more complex pattern is observed, as with sodium sulfate , where the less soluble deca hydrate crystal ( mirabilite ) loses water of crystallization at 32 °C to form a more soluble anhydrous phase ( thenardite ) with a smaller change in Gibbs free energy (Δ G ) in the dissolution reaction. The solubility of organic compounds nearly always increases with temperature. The technique of recrystallization , used for purification of solids, depends on

2496-426: A percentage in this case, and the abbreviation "w/w" may be used to indicate "weight per weight". (The values in g/L and g/kg are similar for water, but that may not be the case for other solvents.) Alternatively, the solubility of a solute can be expressed in moles instead of mass. For example, if the quantity of solvent is given in kilograms , the value is the molality of the solution (mol/kg). The solubility of

2600-406: A percentage, and the abbreviation "v/v" for "volume per volume" may be used to indicate this choice. Conversion between these various ways of measuring solubility may not be trivial, since it may require knowing the density of the solution — which is often not measured, and cannot be predicted. While the total mass is conserved by dissolution, the final volume may be different from both the volume of

2704-448: A plausible source of mud. Another possibility is direct precipitation from the water. A phenomenon known as whitings occurs in shallow waters, in which white streaks containing dispersed micrite appear on the surface of the water. It is uncertain whether this is freshly precipitated aragonite or simply material stirred up from the bottom, but there is some evidence that whitings are caused by biological precipitation of aragonite as part of

2808-449: A radial rather than layered internal structure, indicating that they were formed by algae in a normal marine environment. Peloids are structureless grains of microcrystalline carbonate likely produced by a variety of processes. Many are thought to be fecal pellets produced by marine organisms. Others may be produced by endolithic (boring) algae or other microorganisms or through breakdown of mollusc shells. They are difficult to see in

2912-471: A simple ionic compound (with positive and negative ions) such as sodium chloride (common salt) is easily soluble in a highly polar solvent (with some separation of positive (δ+) and negative (δ-) charges in the covalent molecule) such as water , as thus the sea is salty as it accumulates dissolved salts since early geological ages. The solubility is favored by entropy of mixing (Δ S ) and depends on enthalpy of dissolution (Δ H ) and

3016-510: A solid or liquid can be "dissolved" in a gas only by passing into the gaseous state first. The solubility mainly depends on the composition of solute and solvent (including their pH and the presence of other dissolved substances) as well as on temperature and pressure. The dependency can often be explained in terms of interactions between the particles ( atoms , molecules , or ions ) of the two substances, and of thermodynamic concepts such as enthalpy and entropy . Under certain conditions,

3120-463: A solute's different solubilities in hot and cold solvent. A few exceptions exist, such as certain cyclodextrins . For condensed phases (solids and liquids), the pressure dependence of solubility is typically weak and usually neglected in practice. Assuming an ideal solution , the dependence can be quantified as: where the index i {\displaystyle i} iterates the components, N i {\displaystyle N_{i}}

3224-449: A solvent depends primarily on its polarity . For example, a very polar ( hydrophilic ) solute such as urea is very soluble in highly polar water, less soluble in fairly polar methanol , and practically insoluble in non-polar solvents such as benzene . In contrast, a non-polar or lipophilic solute such as naphthalene is insoluble in water, fairly soluble in methanol, and highly soluble in non-polar benzene. In even more simple terms

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3328-427: A substance in a liquid may also be expressed as the quantity of solute per quantity of solution , rather than of solvent. For example, following the common practice in titration , it may be expressed as moles of solute per litre of solution (mol/L), the molarity of the latter. In more specialized contexts the solubility may be given by the mole fraction (moles of solute per total moles of solute plus solvent) or by

3432-432: Is about half of its value at 25 °C. The dissolution of calcium hydroxide in water is also an exothermic process (Δ H  < 0). As dictated by the van 't Hoff equation and Le Chatelier's principle , lowe temperatures favorsf dissolution of Ca(OH) 2 . Portlandite solubility increases at low temperature. This temperature dependence is sometimes referred to as "retrograde" or "inverse" solubility. Occasionally,

3536-560: Is also favored on the seaward margin of shelves and platforms, where there is upwelling deep ocean water rich in nutrients that increase organic productivity. Reefs are common here, but when lacking, ooid shoals are found instead. Finer sediments are deposited close to shore. The lack of deep sea limestones is due in part to rapid subduction of oceanic crust, but is more a result of dissolution of calcium carbonate at depth. The solubility of calcium carbonate increases with pressure and even more with higher concentrations of carbon dioxide, which

3640-482: Is an uncommon mineral in limestone, and siderite or other carbonate minerals are rare. However, the calcite in limestone often contains a few percent of magnesium . Calcite in limestone is divided into low-magnesium and high-magnesium calcite, with the dividing line placed at a composition of 4% magnesium. High-magnesium calcite retains the calcite mineral structure, which is distinct from dolomite. Aragonite does not usually contain significant magnesium. Most limestone

3744-402: Is carbonate rock, and most of this is limestone. Limestone is found in sedimentary sequences as old as 2.7 billion years. However, the compositions of carbonate rocks show an uneven distribution in time in the geologic record. About 95% of modern carbonates are composed of high-magnesium calcite and aragonite. The aragonite needles in carbonate mud are converted to low-magnesium calcite within

3848-474: Is clusters of peloids cemented together by organic material or mineral cement. Extraclasts are uncommon, are usually accompanied by other clastic sediments, and indicate deposition in a tectonically active area or as part of a turbidity current . The grains of most limestones are embedded in a matrix of carbonate mud. This is typically the largest fraction of an ancient carbonate rock. Mud consisting of individual crystals less than 5 μm (0.20 mils) in length

3952-416: Is commonly white to gray in color. Limestone that is unusually rich in organic matter can be almost black in color, while traces of iron or manganese can give limestone an off-white to yellow to red color. The density of limestone depends on its porosity, which varies from 0.1% for the densest limestone to 40% for chalk. The density correspondingly ranges from 1.5 to 2.7 g/cm . Although relatively soft, with

4056-420: Is controlled largely by the amount of dissolved carbon dioxide ( CO 2 ) in the water. This is summarized in the reaction: Increases in temperature or decreases in pressure tend to reduce the amount of dissolved CO 2 and precipitate CaCO 3 . Reduction in salinity also reduces the solubility of CaCO 3 , by several orders of magnitude for fresh water versus seawater. Near-surface water of

4160-545: Is converted to low-magnesium calcite. Diagenesis is the likely origin of pisoliths , concentrically layered particles ranging from 1 to 10 mm (0.039 to 0.394 inches) in diameter found in some limestones. Pisoliths superficially resemble ooids but have no nucleus of foreign matter, fit together tightly, and show other signs that they formed after the original deposition of the sediments. Silicification occurs early in diagenesis, at low pH and temperature, and contributes to fossil preservation. Silicification takes place through

4264-399: Is defined for specific phases . For example, the solubility of aragonite and calcite in water are expected to differ, even though they are both polymorphs of calcium carbonate and have the same chemical formula . The solubility of one substance in another is determined by the balance of intermolecular forces between the solvent and solute, and the entropy change that accompanies

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4368-503: Is deposited close to where it formed, classification of limestone is usually based on its grain type and mud content. Most grains in limestone are skeletal fragments of marine organisms such as coral or foraminifera . These organisms secrete structures made of aragonite or calcite, and leave these structures behind when they die. Other carbonate grains composing limestones are ooids , peloids , and limeclasts ( intraclasts and extraclasts  [ ca ] ). Skeletal grains have

4472-460: Is described as coquinite . Chalk is a soft, earthy, fine-textured limestone composed of the tests of planktonic microorganisms such as foraminifera, while marl is an earthy mixture of carbonates and silicate sediments. Limestone forms when calcite or aragonite precipitate out of water containing dissolved calcium, which can take place through both biological and nonbiological processes. The solubility of calcium carbonate ( CaCO 3 )

4576-617: Is described as micrite . In fresh carbonate mud, micrite is mostly small aragonite needles, which may precipitate directly from seawater, be secreted by algae, or be produced by abrasion of carbonate grains in a high-energy environment. This is converted to calcite within a few million years of deposition. Further recrystallization of micrite produces microspar , with grains from 5 to 15 μm (0.20 to 0.59 mils) in diameter. Limestone often contains larger crystals of calcite, ranging in size from 0.02 to 0.1 mm (0.79 to 3.94 mils), that are described as sparry calcite or sparite . Sparite

4680-462: Is distinguished from micrite by a grain size of over 20 μm (0.79 mils) and because sparite stands out under a hand lens or in thin section as white or transparent crystals. Sparite is distinguished from carbonate grains by its lack of internal structure and its characteristic crystal shapes. Geologists are careful to distinguish between sparite deposited as cement and sparite formed by recrystallization of micrite or carbonate grains. Sparite cement

4784-667: Is equal to the solubility of the substance. When the dissolution rate of a pure substance is normalized to the surface area of the solid (which usually changes with time during the dissolution process), then it is expressed in kg/m s and referred to as "intrinsic dissolution rate". The intrinsic dissolution rate is defined by the United States Pharmacopeia . Dissolution rates vary by orders of magnitude between different systems. Typically, very low dissolution rates parallel low solubilities, and substances with high solubilities exhibit high dissolution rates, as suggested by

4888-433: Is less than 0.1 g per 100 mL of solvent. Solubility occurs under dynamic equilibrium, which means that solubility results from the simultaneous and opposing processes of dissolution and phase joining (e.g. precipitation of solids ). A stable state of the solubility equilibrium occurs when the rates of dissolution and re-joining are equal, meaning the relative amounts of dissolved and non-dissolved materials are equal. If

4992-497: Is not an instantaneous process. The rate of solubilization (in kg/s) is related to the solubility product and the surface area of the material. The speed at which a solid dissolves may depend on its crystallinity or lack thereof in the case of amorphous solids and the surface area (crystallite size) and the presence of polymorphism . Many practical systems illustrate this effect, for example in designing methods for controlled drug delivery . In some cases, solubility equilibria can take

5096-408: Is observed to be almost an order of magnitude higher (i.e. about ten times higher) when the redox potential is controlled using a highly oxidizing Fe 3 O 4 -Fe 2 O 3 redox buffer than with a moderately oxidizing Ni - NiO buffer. Solubility (metastable, at concentrations approaching saturation) also depends on the physical size of the crystal or droplet of solute (or, strictly speaking, on

5200-560: Is one of the first minerals to precipitate in marine evaporites. Most limestone is formed by the activities of living organisms near reefs, but the organisms responsible for reef formation have changed over geologic time. For example, stromatolites are mound-shaped structures in ancient limestones, interpreted as colonies of cyanobacteria that accumulated carbonate sediments, but stromatolites are rare in younger limestones. Organisms precipitate limestone both directly as part of their skeletons, and indirectly by removing carbon dioxide from

5304-473: Is otherwise chemically fairly pure, with clastic sediments (mainly fine-grained quartz and clay minerals ) making up less than 5% to 10% of the composition. Organic matter typically makes up around 0.2% of a limestone and rarely exceeds 1%. Limestone often contains variable amounts of silica in the form of chert or siliceous skeletal fragments (such as sponge spicules, diatoms , or radiolarians ). Fossils are also common in limestone. Limestone

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5408-472: Is produced by decaying organic matter settling into the deep ocean that is not removed by photosynthesis in the dark depths. As a result, there is a fairly sharp transition from water saturated with calcium carbonate to water unsaturated with calcium carbonate, the lysocline , which occurs at the calcite compensation depth of 4,000 to 7,000 m (13,000 to 23,000 feet). Below this depth, foraminifera tests and other skeletal particles rapidly dissolve, and

5512-518: Is secondary dolomite, formed by chemical alteration of limestone. Limestone is exposed over large regions of the Earth's surface, and because limestone is slightly soluble in rainwater, these exposures often are eroded to become karst landscapes. Most cave systems are found in limestone bedrock. Limestone has numerous uses: as a chemical feedstock for the production of lime used for cement (an essential component of concrete ), as aggregate for

5616-416: Is the ability of a substance , the solute , to form a solution with another substance, the solvent . Insolubility is the opposite property, the inability of the solute to form such a solution. The extent of the solubility of a substance in a specific solvent is generally measured as the concentration of the solute in a saturated solution, one in which no more solute can be dissolved. At this point,

5720-434: Is the mole fraction of the i {\displaystyle i} -th component in the solution, P {\displaystyle P} is the pressure, the index T {\displaystyle T} refers to constant temperature, V i , a q {\displaystyle V_{i,aq}} is the partial molar volume of the i {\displaystyle i} -th component in

5824-421: Is the partial pressure (in atm), and c {\displaystyle c} is the concentration of the dissolved gas in the liquid (in mol/L). The solubility of gases is sometimes also quantified using Bunsen solubility coefficient . In the presence of small bubbles , the solubility of the gas does not depend on the bubble radius in any other way than through the effect of the radius on pressure (i.e.

5928-480: Is used to quantify the solubility of gases in solvents. The solubility of a gas in a solvent is directly proportional to the partial pressure of that gas above the solvent. This relationship is similar to Raoult's law and can be written as: where k H {\displaystyle k_{\rm {H}}} is a temperature-dependent constant (for example, 769.2 L · atm / mol for dioxygen (O 2 ) in water at 298 K), p {\displaystyle p}

6032-497: The critical temperature ), the solubility of ionic solutes tends to decrease due to the change of properties and structure of liquid water; the lower dielectric constant results in a less polar solvent and in a change of hydration energy affecting the Δ G of the dissolution reaction. Gaseous solutes exhibit more complex behavior with temperature. As the temperature is raised, gases usually become less soluble in water (exothermic dissolution reaction related to their hydration) (to

6136-485: The hydrophobic effect . The free energy of dissolution ( Gibbs energy ) depends on temperature and is given by the relationship: Δ G = Δ H – TΔ S . Smaller Δ G means greater solubility. Chemists often exploit differences in solubilities to separate and purify compounds from reaction mixtures, using the technique of liquid-liquid extraction . This applies in vast areas of chemistry from drug synthesis to spent nuclear fuel reprocessing. Dissolution

6240-427: The mass fraction at equilibrium (mass of solute per mass of solute plus solvent). Both are dimensionless numbers between 0 and 1 which may be expressed as percentages (%). For solutions of liquids or gases in liquids, the quantities of both substances may be given volume rather than mass or mole amount; such as litre of solute per litre of solvent, or litre of solute per litre of solution. The value may be given as

6344-412: The reagents have been dissolved in a suitable solvent. Water is by far the most common such solvent. The term "soluble" is sometimes used for materials that can form colloidal suspensions of very fine solid particles in a liquid. The quantitative solubility of such substances is generally not well-defined, however. The solubility of a specific solute in a specific solvent is generally expressed as

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6448-522: The specific surface area or molar surface area of the solute). For quantification, see the equation in the article on solubility equilibrium . For highly defective crystals, solubility may increase with the increasing degree of disorder. Both of these effects occur because of the dependence of solubility constant on the Gibbs energy of the crystal. The last two effects, although often difficult to measure, are of practical importance. For example, they provide

6552-415: The American forces designed bombs that burrowed down 10 metres. Eventually, against these odds, the villagers moved the village to a depth of 30 metres. It was constructed in several stages beginning in 1966 and used until early 1972. The complex grew to include wells, kitchens, rooms for each family and spaces for healthcare. Around sixty families lived in the tunnels; as many as 17 children were born inside

6656-443: The Earth orbit and its rotation axis progressively change and modify the solar irradiance at the Earth surface, temperature starts to increase. When a deglaciation period is initiated, the progressive warming of the oceans releases CO 2 into the atmosphere because of its lower solubility in warmer sea water. In turn, higher levels of CO 2 in the atmosphere increase the greenhouse effect and carbon dioxide acts as an amplifier of

6760-496: The Earth's history. Limestone may have been deposited by microorganisms in the Precambrian , prior to 540 million years ago, but inorganic processes were probably more important and likely took place in an ocean more highly oversaturated in calcium carbonate than the modern ocean. Diagenesis is the process in which sediments are compacted and turned into solid rock . During diagenesis of carbonate sediments, significant chemical and textural changes take place. For example, aragonite

6864-468: The Noyes-Whitney equation. Solubility constants are used to describe saturated solutions of ionic compounds of relatively low solubility (see solubility equilibrium ). The solubility constant is a special case of an equilibrium constant . Since it is a product of ion concentrations in equilibrium, it is also known as the solubility product . It describes the balance between dissolved ions from

6968-430: The accumulation of corals and shells in the sea, have likely been more important for the last 540 million years. Limestone often contains fossils which provide scientists with information on ancient environments and on the evolution of life. About 20% to 25% of sedimentary rock is carbonate rock, and most of this is limestone. The remaining carbonate rock is mostly dolomite , a closely related rock, which contains

7072-434: The base of roads, as white pigment or filler in products such as toothpaste or paint, as a soil conditioner , and as a popular decorative addition to rock gardens . Limestone formations contain about 30% of the world's petroleum reservoirs . Limestone is composed mostly of the minerals calcite and aragonite , which are different crystal forms of calcium carbonate ( CaCO 3 ). Dolomite , CaMg(CO 3 ) 2 ,

7176-657: The beds. This may include the formation of vugs , which are crystal-lined cavities within the limestone. Diagenesis may include conversion of limestone to dolomite by magnesium-rich fluids. There is considerable evidence of replacement of limestone by dolomite, including sharp replacement boundaries that cut across bedding. The process of dolomitization remains an area of active research, but possible mechanisms include exposure to concentrated brines in hot environments ( evaporative reflux ) or exposure to diluted seawater in delta or estuary environments ( Dorag dolomitization ). However, Dorag dolomitization has fallen into disfavor as

7280-482: The bottom with the concave face downwards. This traps a void space that can later be filled by sparite. Geologists use geopetal structures to determine which direction was up at the time of deposition, which is not always obvious with highly deformed limestone formations. The cyanobacterium Hyella balani can bore through limestone; as can the green alga Eugamantia sacculata and the fungus Ostracolaba implexa . Solubility In chemistry , solubility

7384-791: The concentration of a saturated solution of the two. Any of the several ways of expressing concentration of solutions can be used, such as the mass , volume , or amount in moles of the solute for a specific mass, volume, or mole amount of the solvent or of the solution. In particular, chemical handbooks often express the solubility as grams of solute per 100 millilitres of solvent (g/(100 mL), often written as g/100 ml), or as grams of solute per decilitre of solvent (g/dL); or, less commonly, as grams of solute per litre of solvent (g/L). The quantity of solvent can instead be expressed in mass, as grams of solute per 100 grams of solvent (g/(100 g), often written as g/100 g), or as grams of solute per kilogram of solvent (g/kg). The number may be expressed as

7488-471: The concentration of the solute can exceed its usual solubility limit. The result is a supersaturated solution , which is metastable and will rapidly exclude the excess solute if a suitable nucleation site appears. The concept of solubility does not apply when there is an irreversible chemical reaction between the two substances, such as the reaction of calcium hydroxide with hydrochloric acid ; even though one might say, informally, that one "dissolved"

7592-466: The depositional fabric of carbonate rocks. Dunham divides the rocks into four main groups based on relative proportions of coarser clastic particles, based on criteria such as whether the grains were originally in mutual contact, and therefore self-supporting, or whether the rock is characterized by the presence of frame builders and algal mats. Unlike the Folk scheme, Dunham deals with the original porosity of

7696-469: The deposits are highly porous, so that they have a spongelike texture, they are typically described as tufa . Secondary calcite deposited by supersaturated meteoric waters ( groundwater ) in caves is also sometimes described as travertine. This produces speleothems , such as stalagmites and stalactites . Coquina is a poorly consolidated limestone composed of abraded pieces of coral , shells , or other fossil debris. When better consolidated, it

7800-402: The driving force for precipitate aging (the crystal size spontaneously increasing with time). The solubility of a given solute in a given solvent is function of temperature. Depending on the change in enthalpy (Δ H ) of the dissolution reaction, i.e. , on the endothermic (Δ H  > 0) or exothermic (Δ H  < 0) character of the dissolution reaction, the solubility of

7904-406: The earth's oceans are oversaturated with CaCO 3 by a factor of more than six. The failure of CaCO 3 to rapidly precipitate out of these waters is likely due to interference by dissolved magnesium ions with nucleation of calcite crystals, the necessary first step in precipitation. Precipitation of aragonite may be suppressed by the presence of naturally occurring organic phosphates in

8008-493: The extent of solubility for a given application. For example, U.S. Pharmacopoeia gives the following terms, according to the mass m sv of solvent required to dissolve one unit of mass m su of solute: (The solubilities of the examples are approximate, for water at 20–25 °C.) The thresholds to describe something as insoluble, or similar terms, may depend on the application. For example, one source states that substances are described as "insoluble" when their solubility

8112-399: The first refers to the grains and the second to the cement. For example, a limestone consisting mainly of ooids, with a crystalline matrix, would be termed an oosparite. It is helpful to have a petrographic microscope when using the Folk scheme, because it is easier to determine the components present in each sample. Robert J. Dunham published his system for limestone in 1962. It focuses on

8216-572: The formation of distinctive minerals from the silica and clay present in the original limestone. Two major classification schemes, the Folk and Dunham, are used for identifying the types of carbonate rocks collectively known as limestone. Robert L. Folk developed a classification system that places primary emphasis on the detailed composition of grains and interstitial material in carbonate rocks . Based on composition, there are three main components: allochems (grains), matrix (mostly micrite), and cement (sparite). The Folk system uses two-part names;

8320-483: The general warming. A popular aphorism used for predicting solubility is " like dissolves like " also expressed in the Latin language as " Similia similibus solventur ". This statement indicates that a solute will dissolve best in a solvent that has a similar chemical structure to itself, based on favorable entropy of mixing . This view is simplistic, but it is a useful rule of thumb. The overall solvation capacity of

8424-429: The geologic record are called bioherms . Many are rich in fossils, but most lack any connected organic framework like that seen in modern reefs. The fossil remains are present as separate fragments embedded in ample mud matrix. Much of the sedimentation shows indications of occurring in the intertidal or supratidal zones, suggesting sediments rapidly fill available accommodation space in the shelf or platform. Deposition

8528-410: The ocean basins, but limestone is rarely preserved in continental slope and deep sea environments. The best environments for deposition are warm waters, which have both a high organic productivity and increased saturation of calcium carbonate due to lower concentrations of dissolved carbon dioxide. Modern limestone deposits are almost always in areas with very little silica-rich sedimentation, reflected in

8632-672: The other. The solubility is also not the same as the rate of solution , which is how fast a solid solute dissolves in a liquid solvent. This property depends on many other variables, such as the physical form of the two substances and the manner and intensity of mixing. The concept and measure of solubility are extremely important in many sciences besides chemistry, such as geology , biology , physics , and oceanography , as well as in engineering , medicine , agriculture , and even in non-technical activities like painting , cleaning , cooking , and brewing . Most chemical reactions of scientific, industrial, or practical interest only happen after

8736-426: The reaction: Fossils are often preserved in exquisite detail as chert. Cementing takes place rapidly in carbonate sediments, typically within less than a million years of deposition. Some cementing occurs while the sediments are still under water, forming hardgrounds . Cementing accelerates after the retreat of the sea from the depositional environment, as rainwater infiltrates the sediment beds, often within just

8840-482: The relative purity of most limestones. Reef organisms are destroyed by muddy, brackish river water, and carbonate grains are ground down by much harder silicate grains. Unlike clastic sedimentary rock, limestone is produced almost entirely from sediments originating at or near the place of deposition. Limestone formations tend to show abrupt changes in thickness. Large moundlike features in a limestone formation are interpreted as ancient reefs , which when they appear in

8944-460: The rock. The Dunham scheme is more useful for hand samples because it is based on texture, not the grains in the sample. A revised classification was proposed by Wright (1992). It adds some diagenetic patterns to the classification scheme. Travertine is a term applied to calcium carbonate deposits formed in freshwater environments, particularly waterfalls , cascades and hot springs . Such deposits are typically massive, dense, and banded. When

9048-405: The salt and undissolved salt. The solubility constant is also "applicable" (i.e. useful) to precipitation , the reverse of the dissolving reaction. As with other equilibrium constants, temperature can affect the numerical value of solubility constant. While the solubility constant is not as simple as solubility, the value of this constant is generally independent of the presence of other species in

9152-479: The sediments increases. Chemical compaction takes place by pressure solution of the sediments. This process dissolves minerals from points of contact between grains and redeposits it in pore space, reducing the porosity of the limestone from an initial high value of 40% to 80% to less than 10%. Pressure solution produces distinctive stylolites , irregular surfaces within the limestone at which silica-rich sediments accumulate. These may reflect dissolution and loss of

9256-662: The sediments of the ocean floor abruptly transition from carbonate ooze rich in foraminifera and coccolith remains ( Globigerina ooze) to silicic mud lacking carbonates. In rare cases, turbidites or other silica-rich sediments bury and preserve benthic (deep ocean) carbonate deposits. Ancient benthic limestones are microcrystalline and are identified by their tectonic setting. Fossils typically are foraminifera and coccoliths. No pre-Jurassic benthic limestones are known, probably because carbonate-shelled plankton had not yet evolved. Limestones also form in freshwater environments. These limestones are not unlike marine limestone, but have

9360-414: The solubility of gas in the liquid in contact with small bubbles is increased due to pressure increase by Δ p  = 2γ/ r ; see Young–Laplace equation ). Henry's law is valid for gases that do not undergo change of chemical speciation on dissolution. Sieverts' law shows a case when this assumption does not hold. The carbon dioxide solubility in seawater is also affected by temperature, pH of

9464-483: The solubility per mole of solution is usually computed and quoted as if the solute does not dissociate or form complexes—that is, by pretending that the mole amount of solution is the sum of the mole amounts of the two substances. The extent of solubility ranges widely, from infinitely soluble (without limit, i.e. miscible ) such as ethanol in water, to essentially insoluble, such as titanium dioxide in water. A number of other descriptive terms are also used to qualify

9568-453: The solute is not recovered upon evaporation of the solvent, the process is referred to as solvolysis. The thermodynamic concept of solubility does not apply straightforwardly to solvolysis. When a solute dissolves, it may form several species in the solution. For example, an aqueous solution of cobalt(II) chloride can afford [Co(H 2 O) 6 ] , [CoCl(H 2 O) 5 ] , CoCl 2 (H 2 O) 2 , each of which interconverts. Solubility

9672-587: The solution, V i , c r {\displaystyle V_{i,cr}} is the partial molar volume of the i {\displaystyle i} -th component in the dissolving solid, and R {\displaystyle R} is the universal gas constant . The pressure dependence of solubility does occasionally have practical significance. For example, precipitation fouling of oil fields and wells by calcium sulfate (which decreases its solubility with decreasing pressure) can result in decreased productivity with time. Henry's law

9776-573: The solution, and by the carbonate buffer. The decrease of solubility of carbon dioxide in seawater when temperature increases is also an important retroaction factor (positive feedback) exacerbating past and future climate changes as observed in ice cores from the Vostok site in Antarctica . At the geological time scale, because of the Milankovich cycles , when the astronomical parameters of

9880-409: The solvation. Factors such as temperature and pressure will alter this balance, thus changing the solubility. Solubility may also strongly depend on the presence of other species dissolved in the solvent, for example, complex-forming anions ( ligands ) in liquids. Solubility will also depend on the excess or deficiency of a common ion in the solution , a phenomenon known as the common-ion effect . To

9984-415: The solvent and the sum of the two volumes. Moreover, many solids (such as acids and salts ) will dissociate in non-trivial ways when dissolved; conversely, the solvent may form coordination complexes with the molecules or ions of the solute. In those cases, the sum of the moles of molecules of solute and solvent is not really the total moles of independent particles solution. To sidestep that problem,

10088-441: The solvent is removed, all of the substance that had dissolved is recovered. The term solubility is also used in some fields where the solute is altered by solvolysis . For example, many metals and their oxides are said to be "soluble in hydrochloric acid", although in fact the aqueous acid irreversibly degrades the solid to give soluble products. Most ionic solids dissociate when dissolved in polar solvents. In those cases where

10192-630: The tops of hills and seven entrances to the South China Sea . Today, the tunnels are a tourist attraction and can be visited on organised tours. Beside individual tours to the tunnels, they are regularly part of day trips, starting from Huế to explore the DMZ . In comparison to the Củ Chi tunnels further south, walking through the Vinh Moc tunnels is a lot more comfortable, because they are situated in

10296-533: The tunnels and no structural supports are necessary. When the War took place in Vinh Moc from 1965 to 1973, the United States Army released over 9,000 tons of bombs in the area, with a ratio of 7 tons of bombs on average per person. The locals began to dig tunnels in 1965 and finished in 1967 with simple tools in 18,000 labor days. The total length of the tunnels is nearly 2,000 m long with six entrances to

10400-490: The tunnels. The tunnels were a success and no villagers lost their lives. The only direct hit was from a bomb that failed to explode; the resulting hole was utilized as a ventilation shaft. Three levels of tunnels were eventually built. The tunnels lie north of the Bến Hải River . Much of the sub-strata of Vietnam is limestone which is soft to dig through yet structurally sound. The limestone allows easy hand digging of

10504-476: The two substances are said to be at the solubility equilibrium . For some solutes and solvents, there may be no such limit, in which case the two substances are said to be " miscible in all proportions" (or just "miscible"). The solute can be a solid , a liquid , or a gas , while the solvent is usually solid or liquid. Both may be pure substances, or may themselves be solutions. Gases are always miscible in all proportions, except in very extreme situations, and

10608-533: The water by photosynthesis and thereby decreasing the solubility of calcium carbonate. Limestone shows the same range of sedimentary structures found in other sedimentary rocks. However, finer structures, such as lamination , are often destroyed by the burrowing activities of organisms ( bioturbation ). Fine lamination is characteristic of limestone formed in playa lakes , which lack the burrowing organisms. Limestones also show distinctive features such as geopetal structures , which form when curved shells settle to

10712-553: The water. Although ooids likely form through purely inorganic processes, the bulk of CaCO 3 precipitation in the oceans is the result of biological activity. Much of this takes place on carbonate platforms . The origin of carbonate mud, and the processes by which it is converted to micrite, continue to be a subject of research. Modern carbonate mud is composed mostly of aragonite needles around 5 μm (0.20 mils) in length. Needles of this shape and composition are produced by calcareous algae such as Penicillus , making this

10816-416: Was likely deposited in pore space between grains, suggesting a high-energy depositional environment that removed carbonate mud. Recrystallized sparite is not diagnostic of depositional environment. Limestone outcrops are recognized in the field by their softness (calcite and aragonite both have a Mohs hardness of less than 4, well below common silicate minerals) and because limestone bubbles vigorously when

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