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A reaction calorimeter is a calorimeter that measures the amount of energy released (in exothermic reactions) or absorbed (in endothermic reactions) by a chemical reaction. It does this by measuring the total change in temperature of an exact amount of water in a vessel.
Heat flow calorimetry measures the heat flowing across the reactor wall and quantifies this in relation to other energy flows within the reactor.
where:
Heat flow calorimetry allows the user to measure heat while the process temperature remains under control. While the driving force Tr − Tj is measured with a relatively high resolution, the overall heat transfer coefficient U or the calibration factor UA is determined by calibration before and after the reaction takes place. These factors are affected by the product composition, process temperature, agitation rate, viscosity, and liquid level. Using reaction calorimeters accurately requires understanding their limitations and having significant experience with the process. [1]
In heat balance calorimetry, the cooling/heating jacket controls the temperature of the process. Heat is measured by monitoring the heat gained or lost by the heat transfer fluid.
where:
Heat balance calorimetry is considered an effective method for measuring heat, as it involves quantifying the heat entering and leaving the system through the heating/cooling jacket using the heat transfer fluid, whose properties are well known.
This method effectively measures heat loss or gain, circumventing many calibration issues associated with heat flow and power compensation calorimetry. However, it is less effective in traditional batch vessels, where significant heat shifts in the cooling/heating jacket can obscure the process's heat signal. [2]
Power compensation calorimetry is a variation of the heat flow technique. This method utilizes a cooling jacket operating at constant flow and temperature. The process temperature is regulated by adjusting the power of an electrical heater. At the start of the experiment, the electrical heat and cooling power are balanced. As the process's heat load changes, the electrical power is adjusted to maintain the desired process temperature. [3] The heat liberated or absorbed by the process is determined from the difference between the initial electrical power and the electrical power required at the time of measurement. While power compensation calorimetry requires less preparation than heat flow calorimetry, it faces similar limitations. Changes in product composition, liquid level, process temperature, agitation, or viscosity can impact the instrument's calibration. Additionally, the presence of an electrical heating element is not optimal for process operations. Another limitation of this method is that the maximum heat it can measure is equal to the initial electrical power applied to the heater. [4]
where:
Constant flux heating and cooling jackets use variable geometry cooling jackets and can operate with cooling jackets at a substantially constant temperature. These reaction calorimeters are simpler to use and are much more tolerant of changes in the process conditions. [5]
Constant flux calorimetry is an advanced temperature control mechanism used to generate accurate calorimetry. It operates by controlling the jacket area of a laboratory reactor while maintaining a constant inlet temperature of the thermal fluid. This method allows for precise temperature control, even during strongly exothermic or endothermic events, as additional cooling can be achieved by increasing the area over which heat is exchanged.
This system is generally more accurate than heat balance calorimetry, as changes in the delta temperature (Tout - Tin) are magnified by keeping the fluid flow as low as possible.
One of the main advantages of constant flux calorimetry is the ability to dynamically measure heat transfer coefficient (U). According to the heat balance equation:
From the heat flow equation that
These equations can be rearranged to:
This allows for the monitoring of U as a function of time.
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In traditional heat flow calorimeters, one reactant is added continuously in small amounts, similar to a semi-batch process, to achieve complete conversion of the reaction. Unlike in a tubular reactor, this approach results in longer residence times, different substance concentrations, and flatter temperature profiles. Consequently, the selectivity of less well-defined reactions can be affected, potentially leading to the formation of by-products or secondary products. These by-products can alter the measured heat of reaction as different chemical bonds are formed. The amount of by-product or secondary product can be determined by calculating the yield of the desired product.
A continuous reaction calorimeter is a similar instrument used to obtain thermodynamic information on continuous processes in tubular reactors. It can record an axial temperature profile along the tubular reactor, allowing the determination of the specific heat of reaction through heat balances and segmental dynamic parameters. The system typically includes a tubular reactor, dosing systems, preheaters, temperature sensors, and flow meters.
If the heat of reaction measured in the heat flow calorimeter (HFC) differs from that measured in a plug flow reactor (PFR) calorimeter, it is likely that side reactions have occurred. These discrepancies may arise due to differences in temperatures and residence times. The total measured heat (Qr) comprises partially overlapped reaction enthalpies (ΔHr) of both main and side reactions, depending on their degrees of conversion (U).
Continuous reaction calorimeters offer significant advantages in the study of continuous processes, particularly in industrial applications where consistent and reproducible reaction conditions are critical. These instruments can provide detailed insights into the thermodynamics and kinetics of reactions under steady-state conditions. The use of precise dosing systems ensures accurate control over reactant flow rates, while preheaters can stabilize the temperature of incoming reactants, minimizing temperature fluctuations that could affect the reaction rate and selectivity.
Moreover, advanced temperature sensors and flow meters enable real-time monitoring and control of the process parameters, facilitating the optimization of reaction conditions. By recording axial temperature profiles, researchers can identify temperature gradients within the reactor, which can inform adjustments to improve heat transfer efficiency and reaction uniformity. This capability is particularly important in scaling up reactions from laboratory to industrial scale, where maintaining consistent product quality and yield is essential.
Continuous reaction calorimeters also allow for the study of reaction mechanisms and the identification of intermediate species. By analyzing the heat flow data in conjunction with other analytical techniques, such as spectroscopy or chromatography, researchers can gain a comprehensive understanding of the reaction pathways and the factors influencing selectivity and yield. This information is invaluable for developing efficient and sustainable chemical processes, reducing waste, and minimizing energy consumption.
In summary, the integration of continuous reaction calorimeters in chemical research and development provides a robust platform for obtaining precise thermodynamic data, optimizing reaction conditions, and scaling up processes with confidence. Their ability to monitor and control reactions in real-time makes them indispensable tools in the pursuit of innovative and efficient chemical manufacturing.
In chemistry and thermodynamics, calorimetry is the science or act of measuring changes in state variables of a body for the purpose of deriving the heat transfer associated with changes of its state due, for example, to chemical reactions, physical changes, or phase transitions under specified constraints. Calorimetry is performed with a calorimeter. Scottish physician and scientist Joseph Black, who was the first to recognize the distinction between heat and temperature, is said to be the founder of the science of calorimetry.
Enthalpy is the sum of a thermodynamic system's internal energy and the product of its pressure and volume. It is a state function in thermodynamics used in many measurements in chemical, biological, and physical systems at a constant external pressure, which is conveniently provided by the large ambient atmosphere. The pressure–volume term expresses the work that was done against constant external pressure to establish the system's physical dimensions from to some final volume , i.e. to make room for it by displacing its surroundings. The pressure-volume term is very small for solids and liquids at common conditions, and fairly small for gases. Therefore, enthalpy is a stand-in for energy in chemical systems; bond, lattice, solvation, and other chemical "energies" are actually enthalpy differences. As a state function, enthalpy depends only on the final configuration of internal energy, pressure, and volume, not on the path taken to achieve it.
A calorimeter is a device used for calorimetry, or the process of measuring the heat of chemical reactions or physical changes as well as heat capacity. Differential scanning calorimeters, isothermal micro calorimeters, titration calorimeters and accelerated rate calorimeters are among the most common types. A simple calorimeter just consists of a thermometer attached to a metal container full of water suspended above a combustion chamber. It is one of the measurement devices used in the study of thermodynamics, chemistry, and biochemistry.
Conduction is the process by which heat is transferred from the hotter end to the colder end of an object. The ability of the object to conduct heat is known as its thermal conductivity, and is denoted k.
Differential scanning calorimetry (DSC) is a thermoanalytical technique in which the difference in the amount of heat required to increase the temperature of a sample and reference is measured as a function of temperature. Both the sample and reference are maintained at nearly the same temperature throughout the experiment.
A heat exchanger is a system used to transfer heat between a source and a working fluid. Heat exchangers are used in both cooling and heating processes. The fluids may be separated by a solid wall to prevent mixing or they may be in direct contact. They are widely used in space heating, refrigeration, air conditioning, power stations, chemical plants, petrochemical plants, petroleum refineries, natural-gas processing, and sewage treatment. The classic example of a heat exchanger is found in an internal combustion engine in which a circulating fluid known as engine coolant flows through radiator coils and air flows past the coils, which cools the coolant and heats the incoming air. Another example is the heat sink, which is a passive heat exchanger that transfers the heat generated by an electronic or a mechanical device to a fluid medium, often air or a liquid coolant.
The first law of thermodynamics is a formulation of the law of conservation of energy in the context of thermodynamic processes. The law distinguishes two principal forms of energy transfer, heat and thermodynamic work, that modify a thermodynamic system containing a constant amount of matter. The law also defines the internal energy of a system, an extensive property for taking account of the balance of heat and work in the system. Energy cannot be created or destroyed, but it can be transformed from one form to another. In an isolated system the sum of all forms of energy is constant.
Heat transfer is a discipline of thermal engineering that concerns the generation, use, conversion, and exchange of thermal energy (heat) between physical systems. Heat transfer is classified into various mechanisms, such as thermal conduction, thermal convection, thermal radiation, and transfer of energy by phase changes. Engineers also consider the transfer of mass of differing chemical species, either cold or hot, to achieve heat transfer. While these mechanisms have distinct characteristics, they often occur simultaneously in the same system.
The thermoelectric effect is the direct conversion of temperature differences to electric voltage and vice versa via a thermocouple. A thermoelectric device creates a voltage when there is a different temperature on each side. Conversely, when a voltage is applied to it, heat is transferred from one side to the other, creating a temperature difference. At the atomic scale, an applied temperature gradient causes charge carriers in the material to diffuse from the hot side to the cold side.
Joule heating is the process by which the passage of an electric current through a conductor produces heat.
A chemical reactor is an enclosed volume in which a chemical reaction takes place. In chemical engineering, it is generally understood to be a process vessel used to carry out a chemical reaction, which is one of the classic unit operations in chemical process analysis. The design of a chemical reactor deals with multiple aspects of chemical engineering. Chemical engineers design reactors to maximize net present value for the given reaction. Designers ensure that the reaction proceeds with the highest efficiency towards the desired output product, producing the highest yield of product while requiring the least amount of money to purchase and operate. Normal operating expenses include energy input, energy removal, raw material costs, labor, etc. Energy changes can come in the form of heating or cooling, pumping to increase pressure, frictional pressure loss or agitation.
A batch reactor is a chemical reactor in which a non-continuous reaction is conducted, i.e., one where the reactants, products and solvent do not flow in or out of the vessel during the reaction until the target reaction conversion is achieved. By extension, the expression is somehow inappropriately used for other batch fluid processing operations that do not involve a chemical reaction, such as solids dissolution, product mixing, batch distillation, crystallization, and liquid/liquid extraction. In such cases, however, they may not be referred to as reactors but rather with a term specific to the function they perform.
In thermodynamics, the thermal efficiency is a dimensionless performance measure of a device that uses thermal energy, such as an internal combustion engine, steam turbine, steam engine, boiler, furnace, refrigerator, ACs etc.
In chemical thermodynamics, isothermal titration calorimetry (ITC) is a physical technique used to determine the thermodynamic parameters of interactions in solution. It is most often used to study the binding of small molecules to larger macromolecules in a label-free environment. It consists of two cells which are enclosed in an adiabatic jacket. The compounds to be studied are placed in the sample cell, while the other cell, the reference cell, is used as a control and contains the buffer in which the sample is dissolved.
Continuous reactors carry material as a flowing stream. Reactants are continuously fed into the reactor and emerge as continuous stream of product. Continuous reactors are used for a wide variety of chemical and biological processes within the food, chemical and pharmaceutical industries. A survey of the continuous reactor market will throw up a daunting variety of shapes and types of machine. Beneath this variation however lies a relatively small number of key design features which determine the capabilities of the reactor. When classifying continuous reactors, it can be more helpful to look at these design features rather than the whole system.
The Glossary of fuel cell terms lists the definitions of many terms used within the fuel cell industry. The terms in this fuel cell glossary may be used by fuel cell industry associations, in education material and fuel cell codes and standards to name but a few.
In thermodynamics, heat is the thermal energy transferred between systems due to a temperature difference. In colloquial use, heat sometimes refers to thermal energy itself. Thermal energy is the kinetic energy of vibrating and colliding atoms in a substance.
In fluid thermodynamics, a heat transfer fluid is a gas or liquid that takes part in heat transfer by serving as an intermediary in cooling on one side of a process, transporting and storing thermal energy, and heating on another side of a process. Heat transfer fluids are used in countless applications and industrial processes requiring heating or cooling, typically in a closed circuit and in continuous cycles. Cooling water, for instance, cools an engine, while heating water in a hydronic heating system heats the radiator in a room.
The Glossary of Geothermal Heating and Cooling provides definitions of many terms used within the Geothermal heat pump industry. The terms in this glossary may be used by industry professionals, for education materials, and by the general public.
The removal of heat from nuclear reactors is an essential step in the generation of energy from nuclear reactions. In nuclear engineering there are a number of empirical or semi-empirical relations used for quantifying the process of removing heat from a nuclear reactor core so that the reactor operates in the projected temperature interval that depends on the materials used in the construction of the reactor. The effectiveness of removal of heat from the reactor core depends on many factors, including the cooling agents used and the type of reactor. Common liquid coolants for nuclear reactors include: deionized water, heavy water, the lighter alkaline metals, lead or lead-based eutectic alloys like lead-bismuth, and NaK, a eutectic alloy of sodium and potassium. Gas cooled reactors operate with coolants like carbon dioxide, helium or nitrogen but some very low powered research reactors have even been air-cooled with Chicago Pile 1 relying on natural convection of the surrounding air to remove the negligible thermal power output. There is ongoing research into using supercritical fluids as reactor coolants but thus far neither the supercritical water reactor nor a reactor cooled with supercritical Carbon Dioxide nor any other kind of supercritical-fluid-cooled reactor has ever been built.
