It makes a great substitute for toothpaste, can be applied under the arms in place of deodorant, can be mixed with warm water for an antacid, or used as a gargle to help ease coughs and sore throats. Baking soda mixed with water to form a paste and applied to the skin can help sooth insect stings, sunburn, and itching due to poison ivy/oak. There's even some evidence that baking soda may be useful in the prevention and treatment of cancer and kidney disease.
Baking soda can be used to kill cockroaches (fill a shallow dish with equal parts baking soda and granular sugar, place near where you suspect the roaches are) and other insect pests (as a plant spray, combine 2 gallons of water with three tablespoons of baking soda and three tablespoons of cooking oil - spray on plants once a week).
In cleaning, it helps cut through grease, can be used to kill mold and mildew, removes coffee and tea stains, and can freshen the smell of upholstery, carpet, and even pet beds. Got some oil stains on cement or concrete? Sprinkle on some baking soda and scrub with a wet brush to reduce or even eliminate the stain. It can even be used to clean silver and jewelry.
Baking soda can be used as a safe way to extinguish grease and electrical fires. Baking soda mixed with vinegar can help unclog drains and toilets. The uses of baking soda go on and on and on. Just google "uses of baking soda" for many dozens of other ideas.
Vinegar - Vinegar has lots of uses relating to cooking, canning, and food preservation. Its also useful in cleaning, unclogging and deodorizing drains and toilets, disinfecting cutting boards and counter-tops, eliminating mold & mildew, and polishing silver, brass & copper objects.
Vinegar can be used to clean and sanitize canteens, water bottles, thermoses, jars, and other containers. Vinegar can be used to help remove the glue residue of bumper stickers, price tags, and decals. Pouring some vinegar on a rusty screw or hinge can help unstick it. Some folks even use vinegar soaked rags staked in and around their garden to keep out deer, dogs, rabbits, and raccoons, which can't stand the smell even after the vinegar has dried (I've never tried this method myself, so can't vouch for its effectiveness - comment below if you have).
A number of medical studies have shown many health benefits of vinegar, especially apple-cider vinegar, including improving insulin sensitivity and decreasing blood sugar levels (both fasting and post-meal) for folks with prediabetes and type 2 diabetes. My own experience as a type-2 diabetic has convinced me that consuming vinegar with a meal lowers my after-meal blood sugar spike by 25-40%.
As with baking soda, the list of possible uses goes on and on and on. Just google "uses of vinegar" for lots more ideas.
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