JPH0241707B2 - - Google Patents
Info
- Publication number
- JPH0241707B2 JPH0241707B2 JP5621281A JP5621281A JPH0241707B2 JP H0241707 B2 JPH0241707 B2 JP H0241707B2 JP 5621281 A JP5621281 A JP 5621281A JP 5621281 A JP5621281 A JP 5621281A JP H0241707 B2 JPH0241707 B2 JP H0241707B2
- Authority
- JP
- Japan
- Prior art keywords
- ions
- aqueous solution
- ammonium
- carbonate
- bicarbonate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 44
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 40
- 239000007864 aqueous solution Substances 0.000 claims description 35
- -1 ammonium ions Chemical class 0.000 claims description 32
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 27
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 24
- 229910021529 ammonia Inorganic materials 0.000 claims description 22
- 239000001569 carbon dioxide Substances 0.000 claims description 20
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000004817 gas chromatography Methods 0.000 claims description 8
- 238000004445 quantitative analysis Methods 0.000 claims description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 14
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 8
- 235000019270 ammonium chloride Nutrition 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000005979 thermal decomposition reaction Methods 0.000 description 5
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 4
- 239000001099 ammonium carbonate Substances 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000006386 neutralization reaction Methods 0.000 description 4
- 229910000029 sodium carbonate Inorganic materials 0.000 description 4
- 238000004448 titration Methods 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 238000001256 steam distillation Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 2
- 235000012501 ammonium carbonate Nutrition 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011736 potassium bicarbonate Substances 0.000 description 2
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 2
- 235000015497 potassium bicarbonate Nutrition 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 2
- 238000002798 spectrophotometry method Methods 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VRZJGENLTNRAIG-UHFFFAOYSA-N 4-[4-(dimethylamino)phenyl]iminonaphthalen-1-one Chemical compound C1=CC(N(C)C)=CC=C1N=C1C2=CC=CC=C2C(=O)C=C1 VRZJGENLTNRAIG-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000011181 potassium carbonates Nutrition 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
- G01N31/002—Determining nitrogen by transformation into ammonia, e.g. KJELDAHL method
Landscapes
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Molecular Biology (AREA)
- Physics & Mathematics (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analyzing Non-Biological Materials By The Use Of Chemical Means (AREA)
Description
本発明は、水溶液中のアンモニウムイオンを簡
便迅速に定量する方法に関する。
従来、水溶液中のアンモニウムイオンをアンモ
ニアにまで分解するのに、一般に水酸化ナトリウ
ム等の強アルカリを添加して、水蒸気蒸留する方
法が採られているが、この方法では、水蒸気蒸留
装置を必要とするばかりでなく、操作も煩雑で、
しかも水蒸気蒸留に20分以上要する。
他方、水溶液中のアンモニウムイオンを水溶液
の状態で定量分析する方法として、中和滴定法、
及びネスラー法、インドフエノールブルー法の吸
光光度法、イオン選択性電極法等がある。しかし
ながら、中和滴定法、吸光光度法は、水溶液中に
共存物質が多い場合には正確な分析値を得ること
ができない欠点があるばかりでなく、自動分析計
として採用するには装置が高価過ぎる欠点もあ
る。一方、イオン選択性電極法は、ppmレベルの
微量のアンモニウムイオンの定量に最近利用され
つつあるが、高濃度のアンモニウムイオンの定量
では精度が悪く、その利用範囲が制限されてい
る。
本発明者らは、かかる従来法の欠点を解決すべ
く鋭意研究を積み重ねた結果、水溶液中のアンモ
ニウムイオンの定量に適した簡便で迅速な定量法
を見い出し、本発明は完成させたものである。水
溶液中のアンモニウムイオンを定量するに際し、
該水溶液を水溶液中の炭酸イオン／アンモニウム
イオン（モル比）が0.5以上になる量の炭酸イオ
ンの存在下に加熱して発生するアンモニアまたは
二酸化炭素、若しくは該水溶液を水溶液中の重炭
酸イオン／アンモニウムイオン（モル比）が１以
上になる量の重炭酸イオンの存在下に加熱して発
生するアンモニアを定量することを特徴とする水
溶液中のアンモニウムイオンの定量法である。本
発明の方法を使用すると、(1)本来の分解温度より
低い約100℃以上の温度で、水溶液中のアンモニ
ウムイオンを炭酸イオン、重炭酸イオンを存在さ
せることによりアンモニアと二酸化炭素に分解で
きる、(2)炭酸イオンを存在させる場合、ガスクロ
マトグラフイーで簡単に分析できる二酸化炭素を
定量することにより、間接的アンモニウムイオン
が定量できる、(3)従来のアルカリによる水蒸気蒸
留が不要となるので測定時間がはるかに短かく、
測定操作も簡単で、高濃度のアンモニウムイオン
でも正確に測定できる、(4)製造現場の工程管理分
析に容易に適用できる、等の効果を発揮できる。
アンモニウムイオンは、水溶液中では一般に塩
素イオン、炭酸イオン、重炭酸イオン、硫酸イオ
ン、硝酸イオン等の陰イオンおよびナトリウム、
カリウム等を陽イオンとして共存している場合が
多い。本発明方法では、上記のような共存イオン
が存在していても、熱分解で発生するアンモニア
を定量すれば、共存イオンの影響がないことが分
つた。しかし、炭酸イオン、重炭酸イオンが共存
する場合には、熱分解で発生する炭酸ガスを定量
し、それから逆算してアンモニウムイオンを定量
する方法をそのまま用いたのでは、測定誤差が大
きくなることがある。この場合には、アンモニウ
ムイオンを含有する水溶液のPHを７〜９、特に８
付近に予め調整することにより、炭酸イオンの影
響を避けることができる。すなわち、水溶液のPH
が高いと、アンモニウムイオンが水酸化アンモニ
ウムまたは溶存アンモニアとなつて、炭酸イオ
ン、重炭酸イオンを添加しても炭酸アンモニウ
ム、重炭酸アンモニウムとならず一方PHが低い
と、炭酸イオンも重炭酸イオンに変化し、こうし
た水溶液中の重炭酸イオン自身が分解して二酸化
炭素を発生させるのであろうと推定される。
本発明では、アンモニウムイオンを含む水溶液
に炭酸イオン、重炭酸イオンを存在させることが
極めて重要である。即ち、炭酸イオン、重炭酸イ
オンを存在させることにより、今まで、塩素イオ
ン、硫酸イオン等と共存していたアンモニウムイ
オンが約100℃付近という驚くべき低温でアンモ
ニアに分解することになつた。このことは、恐ら
く炭酸イオン、重炭酸イオンが水溶液中のアンモ
ニウムイオンと、室温、又は加温下に反応し、熱
分解温度の低い化合物である炭酸アンモニウム、
または重炭酸アンモニウムに変化したためであろ
うと思われる。
本発明で使用される炭酸イオン、重炭酸イオン
は、水溶性の炭酸塩、または重炭酸塩であれば特
に制限ないが、一般には、炭酸ナトリウム、炭酸
カリウム、重炭酸ナトリウム、重炭酸カリウム等
である。但し、二酸化炭素から間接的にアンモニ
ウムイオンを定量する場合には、重炭酸ナトリウ
ム、重炭酸カリウム等の重炭酸塩の添加は、過剰
の重炭酸イオンが分解して二酸化炭素を発生させ
ることがあるので避けねばならない。なお炭酸イ
オンを存在させる場合、その存在量は、水溶液中
の炭酸イオン／アンモニウムイオン（モル比）が
0.5以上になる量であれば十分である。また、重
炭酸イオンを存在させる場合は、その存在量は、
水溶液中の重炭酸イオン／アンモニウムイオン
（モル比）が１以上になる量であれば十分である。
したがつて、アンモニウムイオンを含む水溶液中
に既に炭酸イオン、重炭酸イオンが混入している
場合にはその量だけ、炭酸イオン、重炭酸イオン
の添加量を少くすることができる。水溶液中の炭
酸イオン／アンモニウムイオン（モル比）を0.5
以上、又は水溶液中の重炭酸イオン／アンモニウ
ムイオン（モル比）を１以上に保つと、100℃以
上に加熱することにより、水溶液中のアンモニウ
ムイオンを100℃分解させることができる。水溶
液中の炭酸イオン／アンモニウムイオン（モル
比）が0.5未満、又は水溶液中の重炭酸イオン／
アンモニウムイオン（モル比）が１未満では、水
溶液中のアンモニウムイオンが該炭酸イオン量に
相当する分しか分解せず、100％分解しない。
本発明方法では、アンモニウムイオンを含む水
溶液に炭酸イオンを存在させた後、加熱すること
により、アンモニウムイオンをアンモニアと、ア
ンモニウムイオンと当量の二酸化炭素として発生
させ、そのアンモニア、または二酸化炭素を定
量、若しくはアンモニウムイオンを含む水溶液に
重炭酸イオンを存在させた後、加熱することによ
り発生するアンモニアを定量するものである。そ
の加熱する装置は特に限定されず、100℃以上に
加熱し、発生するアンモニア、または二酸化炭素
を回収できる装置であれば、従来公知のものが制
限なく採用される。また、発生したアンモニア、
または二酸化炭素の定量方法（装置）も特に制限
されず、ガスクロマトグラフイー、オルザツト
法、赤外線吸収法などが好適に採用される。
本発明方法でガスクロマトグラフイーを用いる
場合には、試料気化室の温度を300℃以上に保つ
ことによつて、アンモニウムイオンが定量的にア
ンモニアおよび二酸化炭素に分解され、得られた
ガスクロマトグラムもシヤープなアンモニアおよ
び二酸化炭素のピークを与えた。ガスクロマトグ
ラフイーの分離カラムには、アンモニアを定量す
る場合にはアンモニアが、二酸化炭素を定量する
場合には二酸化炭素が、それぞれ、空気、水等の
他の成分と分離できる充填剤が用いられているも
のであれば、制限なく使用される。一般には、水
の溶出が短時間で終るポーラスポリマー系の充填
剤が好都合であり、アンモニアを定量する場合に
はトリエタノールアミンをコーテイングしたポラ
パツクＲ（商品名）が、二酸化炭素を定量する場
合にはポラパツクＲが好適に使用される。その他
のガスクロマトグラフイーの測定条件は、通常の
分析条件がそのまま本発明にも適用される。
本発明を更に実施例に基づいて具体的に説明す
るが、本発明はこれらの実施例のみに限定される
ものではない。
実施例 １
塩化アンモニウム標準溶液（10ｇ／100ml）10
mlを100mlメスフラスコに採取しそれに炭酸ナト
リウム２ｇ（炭酸イオン／アンモニウムイオンの
モル比は約１）を添加溶解し、水で100mlとした。
この溶液5μをマイクロシリンジに採り、下記
の条件に設定されたガスクロマトグラフイーに注
入して熱分解して発生したアンモニアのピーク面
積を求めた。
ガスクロマトグラフイー条件
分離カラム；トリエタノールアミン20％コーテ
イングしたポラパツクＲ、内径２mm、長さ
2m
カラム温度；70℃
注入口温度；300℃
検出器温度；150℃
キヤリアーガス；水素40ml／min
検出器；熱伝導度型（TCD）170mA
次いで、予め塩化アンモニウムと炭酸ナトリウ
ムにより求めた検量線を用いて、該ピーク面積か
ら溶液中の塩化アンモニウム量を算出した結果を
第１表に示した。第１表には、比較のために、同
一試料を水酸化ナトリウムで分解し、アンモニウ
ムイオンを分解するに消費された水酸化ナトリウ
ムを塩酸で中和して求めた中和滴定法による塩化
アンモニウム量も示した。
The present invention relates to a method for simply and quickly quantifying ammonium ions in an aqueous solution. Conventionally, to decompose ammonium ions in an aqueous solution into ammonia, a strong alkali such as sodium hydroxide is generally added and steam distilled, but this method requires a steam distillation device. Not only is it difficult to use, but it is also complicated to operate.
Moreover, steam distillation takes more than 20 minutes. On the other hand, as a method for quantitatively analyzing ammonium ions in an aqueous solution, neutralization titration method,
There are also the Nessler method, the indophenol blue method, the spectrophotometric method, and the ion-selective electrode method. However, the neutralization titration method and spectrophotometry method not only have the disadvantage that accurate analytical values cannot be obtained when there are many coexisting substances in the aqueous solution, but also the equipment is too expensive to be used as an automatic analyzer. There are also drawbacks. On the other hand, the ion-selective electrode method has recently been used to quantify trace amounts of ammonium ions at the ppm level, but its accuracy is poor in quantifying ammonium ions at high concentrations, limiting its range of use. As a result of intensive research aimed at solving the drawbacks of such conventional methods, the present inventors have discovered a simple and rapid quantitative method suitable for quantifying ammonium ions in aqueous solutions, and have completed the present invention. . When quantifying ammonium ions in an aqueous solution,
Ammonia or carbon dioxide generated by heating the aqueous solution in the presence of carbonate ions in an amount such that the carbonate ion/ammonium ion (molar ratio) in the aqueous solution is 0.5 or more, or the bicarbonate ion/ammonium ion in the aqueous solution. This is a method for quantifying ammonium ions in an aqueous solution, which is characterized by quantifying ammonia generated by heating in the presence of bicarbonate ions in an amount such that the ions (molar ratio) are 1 or more. By using the method of the present invention, (1) ammonium ions in an aqueous solution can be decomposed into ammonia and carbon dioxide in the presence of carbonate ions and bicarbonate ions at a temperature of about 100°C or higher, which is lower than the original decomposition temperature; (2) When carbonate ions are present, ammonium ions can be indirectly quantified by quantifying carbon dioxide, which can be easily analyzed by gas chromatography; (3) Measurement time is reduced because conventional steam distillation using alkali is not required. is much shorter,
The measurement operation is simple, and even high concentrations of ammonium ions can be measured accurately. (4) It can be easily applied to process control analysis at manufacturing sites. In aqueous solutions, ammonium ions generally contain anions such as chloride ions, carbonate ions, bicarbonate ions, sulfate ions, and nitrate ions, as well as sodium,
Potassium and other substances often coexist as cations. In the method of the present invention, even if the above-mentioned coexisting ions are present, it has been found that there is no effect of the coexisting ions when ammonia generated by thermal decomposition is quantified. However, when carbonate ions and bicarbonate ions coexist, using the method of quantifying carbon dioxide gas generated by thermal decomposition and then calculating back to quantify ammonium ions may result in large measurement errors. be. In this case, the pH of the aqueous solution containing ammonium ions should be adjusted to 7 to 9, especially 8.
The influence of carbonate ions can be avoided by adjusting the temperature in the vicinity in advance. That is, the PH of the aqueous solution
When pH is high, ammonium ions become ammonium hydroxide or dissolved ammonia, and even if carbonate ions and bicarbonate ions are added, they do not become ammonium carbonate or ammonium bicarbonate. On the other hand, when pH is low, carbonate ions also become bicarbonate ions. It is presumed that the bicarbonate ions in the aqueous solution decompose themselves and generate carbon dioxide. In the present invention, it is extremely important to have carbonate ions and bicarbonate ions present in the aqueous solution containing ammonium ions. That is, due to the presence of carbonate ions and bicarbonate ions, ammonium ions, which had previously coexisted with chloride ions, sulfate ions, etc., were decomposed into ammonia at a surprisingly low temperature of around 100°C. This probably means that carbonate ions and bicarbonate ions react with ammonium ions in an aqueous solution at room temperature or under heating, and ammonium carbonate, a compound with a low thermal decomposition temperature,
Or it may be due to conversion to ammonium bicarbonate. The carbonate ions and bicarbonate ions used in the present invention are not particularly limited as long as they are water-soluble carbonates or bicarbonates, but generally include sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, etc. be. However, when quantifying ammonium ions indirectly from carbon dioxide, adding bicarbonate such as sodium bicarbonate or potassium bicarbonate may cause excess bicarbonate ions to decompose and generate carbon dioxide. Therefore, it must be avoided. When carbonate ions are present, their abundance is determined by the carbonate ion/ammonium ion (molar ratio) in the aqueous solution.
An amount of 0.5 or more is sufficient. In addition, if bicarbonate ions are present, their abundance is
It is sufficient that the amount makes the bicarbonate ion/ammonium ion (molar ratio) in the aqueous solution 1 or more.
Therefore, when carbonate ions and bicarbonate ions are already mixed in the aqueous solution containing ammonium ions, the amount of carbonate ions and bicarbonate ions added can be reduced by that amount. Carbonate ion/ammonium ion (molar ratio) in aqueous solution is 0.5
If the above or the bicarbonate ion/ammonium ion (molar ratio) in the aqueous solution is kept at 1 or more, ammonium ions in the aqueous solution can be decomposed at 100°C by heating to 100°C or higher. Carbonate ion/ammonium ion (molar ratio) in the aqueous solution is less than 0.5, or bicarbonate ion/ammonium ion in the aqueous solution
If the ammonium ion (molar ratio) is less than 1, the ammonium ions in the aqueous solution are decomposed only in an amount corresponding to the amount of carbonate ions, not 100%. In the method of the present invention, after carbonate ions are present in an aqueous solution containing ammonium ions, ammonium ions are generated as ammonia and carbon dioxide equivalent to the ammonium ions by heating, and the ammonia or carbon dioxide is quantitatively determined. Alternatively, ammonia generated by making bicarbonate ions exist in an aqueous solution containing ammonium ions and then heating the solution is quantified. The heating device is not particularly limited, and any conventionally known device can be used without restriction as long as it can heat the device to 100° C. or higher and recover the generated ammonia or carbon dioxide. In addition, ammonia generated,
Also, the method (device) for quantifying carbon dioxide is not particularly limited, and gas chromatography, Orsatz method, infrared absorption method, etc. are suitably employed. When gas chromatography is used in the method of the present invention, ammonium ions are quantitatively decomposed into ammonia and carbon dioxide by keeping the temperature of the sample vaporization chamber above 300°C, and the resulting gas chromatogram is also sharp. gave ammonia and carbon dioxide peaks. Gas chromatography separation columns use packing materials that can separate ammonia when quantifying ammonia and carbon dioxide from other components such as air and water when quantifying carbon dioxide. It can be used without restriction if it exists. In general, porous polymer-based fillers are convenient because they allow water to be eluted in a short period of time, and when quantifying ammonia, Polapack R (trade name) coated with triethanolamine is suitable for quantifying carbon dioxide. Polapack R is preferably used. As for other gas chromatography measurement conditions, the usual analysis conditions are also applied to the present invention as they are. The present invention will be further explained in detail based on Examples, but the present invention is not limited only to these Examples. Example 1 Ammonium chloride standard solution (10g/100ml) 10
ml was collected in a 100 ml volumetric flask, 2 g of sodium carbonate (molar ratio of carbonate ions/ammonium ions was approximately 1) was added and dissolved therein, and the volume was made up to 100 ml with water.
5μ of this solution was taken into a microsyringe and injected into a gas chromatograph set under the following conditions to determine the peak area of ammonia generated by thermal decomposition. Gas chromatography conditions Separation column: Polapack R coated with 20% triethanolamine, inner diameter 2 mm, length
2m Column temperature: 70℃ Inlet temperature: 300℃ Detector temperature: 150℃ Carrier gas: Hydrogen 40ml/min Detector: Thermal conductivity type (TCD) 170mA Next, the calibration curve determined in advance using ammonium chloride and sodium carbonate was calculated. Table 1 shows the results of calculating the amount of ammonium chloride in the solution from the peak area. For comparison, Table 1 shows the amount of ammonium chloride obtained by neutralization titration method, which was determined by decomposing the same sample with sodium hydroxide and neutralizing the sodium hydroxide consumed in decomposing ammonium ions with hydrochloric acid. was also shown.
【表】
実施例 ２
実施例１で調整した試料溶液2μをマイクロ
シリンジに採り、下記の条件に設定されたガスク
ロマトグラフイーに注入して、熱分解して発生し
た二酸化炭素のピーク面積を求めた。次いで、予
め塩化アンモニウムと炭酸ナトリウムにより求め
た検量線を用いて、該ピーク面積から、溶液中の
塩化アンモニウム量を算出した結果を第２表に示
した。
ガスクロマトグラフイー条件
分離カラム；ポラパツクＲ、内径３mm、長さ
3m
カラム温度；120℃
注入口温度；300℃
検出器温度；200℃
キヤリヤーガス；水素50ml／min
検出器；熱伝導度型（TCD）120mA[Table] Example 2 2μ of the sample solution prepared in Example 1 was taken into a microsyringe and injected into a gas chromatograph set under the following conditions to determine the peak area of carbon dioxide generated by thermal decomposition. . Next, the amount of ammonium chloride in the solution was calculated from the peak area using a calibration curve previously determined using ammonium chloride and sodium carbonate, and the results are shown in Table 2. Gas chromatography conditions Separation column: Pola Pack R, inner diameter 3 mm, length
3m Column temperature: 120℃ Inlet temperature: 300℃ Detector temperature: 200℃ Carrier gas: Hydrogen 50ml/min Detector: Thermal conductivity type (TCD) 120mA
【表】【table】
【表】
実施例 ３
実施例１、２において、試料として塩化アンモ
ニウム標準溶液の代りに、製造工程液（塩素イオ
ン３〜8mol／、アンモニウムイオン３〜
8mol／、炭酸イオン0.5〜3mol／）を用いた
他は、実施例１、２と全く同様に実施した結果を
第３表に示した。第３表には比較のために、同一
試料に水酸化ナトリウムを添加、水蒸気蒸留し、
発生したアンモニアを中和滴定法により求めた定
量値も示した。[Table] Example 3 In Examples 1 and 2, instead of the ammonium chloride standard solution as the sample, the manufacturing process solution (3 to 8 mol/chlorine ion, 3 to 8 mol/ammonium ion) was used as the sample.
Table 3 shows the results of carrying out the experiment in exactly the same manner as in Examples 1 and 2, except that 8 mol/carbonate ion and 0.5 to 3 mol/carbonate ion were used. For comparison, Table 3 shows the same sample with sodium hydroxide added and steam distilled.
Quantitative values of generated ammonia determined by neutralization titration are also shown.
Claims (1)
際し、該水溶液を水溶液中の炭酸イオン／アンモ
ニウムイオン（モル比）が0.5以上になる量の炭
酸イオンの存在下に加熱して発生するアンモニア
または二酸化炭素、若しくは該水溶液を水溶液中
の重炭酸イオン／アンモニウムイオン（モル比）
が１以上になる量の重炭酸イオンの存在下に加熱
して発生するアンモニアを定量することを特徴と
する水溶液中のアンモニウムイオンの定量法。 ２ 発生したアンモニアまたは二酸化炭素をガス
クロマトグラフイーで定量する特許請求の範囲第
１項記載の定量法。 ３ 加熱温度が100℃以上である特許請求の範囲
第１項記載の定量法。 ４ 水溶液中のPHを予め７〜９に調整したのち炭
酸イオンの存在下に加熱して発生する二酸化炭素
を定量する特許請求の範囲第１項記載の定量法。[Claims] 1. When quantifying ammonium ions in an aqueous solution, the aqueous solution is generated by heating the aqueous solution in the presence of carbonate ions in an amount such that the carbonate ion/ammonium ion (molar ratio) in the aqueous solution is 0.5 or more. Ammonia or carbon dioxide, or bicarbonate ion/ammonium ion in aqueous solution (molar ratio)
1. A method for quantifying ammonium ions in an aqueous solution, which comprises quantifying ammonia generated by heating in the presence of bicarbonate ions in an amount of 1 or more. 2. The quantitative method according to claim 1, in which the generated ammonia or carbon dioxide is determined by gas chromatography. 3. The quantitative method according to claim 1, wherein the heating temperature is 100°C or higher. 4. The quantitative method according to claim 1, wherein the pH of the aqueous solution is adjusted in advance to 7 to 9, and then heated in the presence of carbonate ions to determine the amount of carbon dioxide generated.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5621281A JPS57171256A (en) | 1981-04-16 | 1981-04-16 | Determination of ammonium ion in water solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5621281A JPS57171256A (en) | 1981-04-16 | 1981-04-16 | Determination of ammonium ion in water solution |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS57171256A JPS57171256A (en) | 1982-10-21 |
| JPH0241707B2 true JPH0241707B2 (en) | 1990-09-19 |
Family
ID=13020796
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5621281A Granted JPS57171256A (en) | 1981-04-16 | 1981-04-16 | Determination of ammonium ion in water solution |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS57171256A (en) |
-
1981
- 1981-04-16 JP JP5621281A patent/JPS57171256A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS57171256A (en) | 1982-10-21 |
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